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546 


65-40572 
65-40572 


546 

Weeks 

Discovery  of  the  elements 


KANSAS  CITY.  MO.  PUBLIC  UBRARY 


D  DDD1  020621? 


MAY  0 


Discovery 
of  the  Elements 


;DUC  ATION 


Discovery  of 


>TH  EDITION 


Published  by  the 


the  Elements 


by  MARY  ELVIRA  WEEKS 


Edited,  with  a  chapter  on 
Elements  Discovered  by  Atomic  Bombardment, 

by  HENRY  M.  LEICESTER,  Ph.D. 

College  of  Physicians  and  Surgeons 
San  Francisco,  California 


Illustrations  collected  by  F,  B.  DAINS 

Professor  of  Chemistry 
University  of  Kansas 


JOURNAL  OF  CHEMICAL  EDUCATION 


@  Copyright,  1956,  btf  the 

Journal  of  Chemical  Education,  Easton,  Pa. 

Library  of  Congress  Catalog  Card  No.:  56-6382 


SIXTH  EDITION 
Enlarged  and  Revised 
Second  Printing,  1960 


Printed  in  the  United  States  of  America  by  the 
Mack  Printing  Company,  Easton,  Pa, 


Foreword 


he  material  blessings  that  man  enjoys  today  have  re 
sulted  largely  from  his  ever-increasing  knowledge  of  about  one 
hundred  simple  substances,  the  chemical  elements,  most  of  which 
were  entirely  unknown  to  ancient  civilizations.  In  the  luxurious 
thermas  of  the  Roman  patrician,  with  all  their  lavish  display  of 
alabaster  floors,  porphyry  walls,  marble  stairs,  and  mosaic  ceil 
ings,  no  nickel-plated  or  chromium  fixtures  were  to  be  seen; 
among  his  artistic  golden  bowls  and  goblets  no  platinum  or 
tantalum  objects  were  ever  to  be  found;  with  all  his  spoils  of 
war  he  could  not  buy  the  smallest  aluminum  trinket. 

Even  the  haughtiest  Roman  conqueror  was  earthbound,  for 
he  knew  no  light  metal  like  aluminum  or  magnesium  and  no 
light  gas  like  hydrogen  or  helium  to  make  lofty  flight  possible. 
Without  a  lantern  in  his  hand,  he  could  not  walk  along  the 
splendid  lava  pavements  of  the  city  streets  at  night,  for  the  white 
glow  of  the  tungsten  filament  and  the  crimson  glow  of  the  neon 
tube  were  lacking.  The  water  that  came  to  him  from  mountain 
springs,  lakes,  and  rivers  through  miles  of  magnificent  aqueducts 
was  a  menace  to  health,  for  there  was  no  chlorine  with  which  to 
kill  the  bacteria.  When  accident  befell  him,  there  was  no  iodine 
for  the  healing  of  the  wound;  when  he  lay  gasping  for  breath, 
no  cylinder  of  oxygen  to  save  him. 

The  story  of  the  disclosure,  one  by  one,  of  the  chemical 
elements  has  never  been  told  as  a  connected  narrative.  The  re 
ports  of  these  discoveries  and  the  life  stories  of  the  discoverers 
are  recorded  for  the  most  part  in  old  chemical  journals,  bio 
graphical  dictionaries,  old  letters,  and  obsolete  textbooks  that  are 
seldom  read  by  the  busy  modern  chemist.  It  is  hoped,  therefore, 
that  these  chapters  may  not  only  render  tribute  to  the  honored 
men  and  women  who  helped  to  reveal  the  hidden  chemical  ele 
ments,  but  may  also  serve  to  acquaint  chemists  and  others  with 
these  great  achievements. 

The  task  of  selecting  and  eliminating  material, has  been 
pleasant  but  difficult,  It  has  frequently  happened  that  two  or 
more  men  have  discovered  the  same  element  independently,  In 
other  instances  various  observers  have  recognized  the  existence 
of  a  new  element  long  before  it  was  actually  isolated.  In  such 

CITY  (1C,.  PIZoLIC  IIBNAKT 

65405?^ 


Vi  DISCOVERY  OF   THE  ELEMENTS 

cases  an  attempt  has  been  made  to  relate  all  important  steps  in 
the  discovery  as  fairly  and  completely  as  possible  without 
ascribing  the  honor  of  discovery  to  any  one  person. 

If  the  reader  is  led  through  closer  acquaintance  with  the  dis 
coverers  of  the  chemical  elements  to  a  deeper  appreciation  of 
their  glorious  achievements,  the  book  has  not  been  written  in 
vain. 

It  is  a  pleasure  to  acknowledge  the  kind  assistance  given  by 
Dr.  E.  H.  S.  Bailey  and  Dr.  Selma  Gottlieb  Kallis?  who  read 
portions  of  the  manuscript,  by  Dr.  F.  B.  Dains,  who  made  many 
helpful  suggestions  as  to  sources  of  material  and  furnished  most 
of  the  illustrations,  by  Dr.  Max  Speter,  who  read  the  proof  for 
the  fourth  edition,  and  by  Dr.  Henry  M.  Leicester,  who  read  the 
manuscript  of  the  sixth  edition  and  wrote  the  chapter  on  "Ele 
ments  Discovered  by  Atomic  Bombardment." 

Grateful  acknowledgment  is  given  to  Mr.  Oren  Bingham, 
who  made  most  of  the  photographic  reproductions  for  the  first 
edition.  The  generous  cooperation  of  the  library  staff  and 
graduate  research  committee  at  The  University  of  Kansas,  the 
Edgar  Fahs  Smith  Memorial  Library,  the  former  Austro-Ameri- 
can  Institute  of  Education,  Science  Service,  and  the  Journal  of 
Chemical  Education  is  deeply  appreciated.  The  publication 
of  valuable  illustrations  was  made  possible  through  the  courtesy 
of  the  Aluminum  Co.  of  America,  the  library  of  the  American 
Philosophical  Society,  the  Army  Medical  Library,  the  Bausch 
and  Lomb  Optical  Co.,  the  Central  Scientific  Co.,  Cornell  Uni 
versity,  the  Ecole  Superieure  des  Mines  at  Paris,  the  Fansteel 
Products  Co.,  tiie  Fisher  Scientific  Co.,  the  Franklin  Institute, 
Gauthier-Villars  et  Cie.,  Harvard  University,  The  Johns  Hopkins 
University,  Lehigh  University  Library,  Macmillan  and  Co., 
Masson  et  Cie.,  the  McGraw-Hill  Book  Co.,  the  Arthur  Nemayer 
Buchdruckerei  und  Verlag,  the  Royal  Library  of  Stockholm,  the 
Scientific  American.,  the  Scientific  Monthly.,  and  the  University 
of  New  Hampshire.  The  author  wishes  to  thank  Mr.  M.  K.  Elias 
and  Miss  Mary  Larson  for  the  Russian  and  some  of  the  Swedish 
translations.  The  kind  cooperation  of  the  following  persons  who 
assisted  in  the  search  for  illustrations  and  other  historical  mate 
rial  is  also  acknowledged  with  pleasure:  Dr.  Fred  Allison,  Miss 
Eva  Armstrong,  Mr.  A.  S.  Banciu,  Prof.  Modesto  Bargallo,  Dr. 
William  H.  Barnes,  Prof.  Gabriel  Bertrand,  Mr.  Carl  Bjorkbom, 
Dr.  C.  A.  Browne,  Dr.  Otto  Brunck,  Senor  B.  J.  Caycedo,  Dr. 
Fritz  Chemnitius,  Dr.  F.  G.  Corning,  Dr.  Dick  Coster,  Mr.  James 
M.  Crowe,  Dr.  Tenney  L.  Davis,  Dr.  Claude  K.  Deischer,  Dr. 


FOREWORD  Vll 


Leonard  Dobbin,  Dr.  A.  S.  Eve,  Dr.  P.  V.  Faragher,  Miss  M.  Eliza 
beth  Farson,  Dr.  A.  Fleck,  Dr.  F.  Fiala,  Mr.  Allyn  B.  Forbes,  M. 
Freymann,  Senor  A.  de  Galvez-Cafiero,  Dr.  Neil  E.  Gordon,  Dr. 
A.  V.  Grosse,  Dr.  W.  A.  Hamor,  Mrs.  Gertrude  D.  Hess,  Dr.  J. 
Heyrovsky,  Mr.  Douglas  B.  Hobbs,  Dr.  H.  N.  Holmes,  Dr.  B. 
Smith  Hopkins,  Sir  James  C.  Irvine,  Mme.  Y.  Khouvine,  Dr.  Gra 
ham  Lusk,  Dr.  L.  W.  McCay,  Dr.  E.  V.  McCollum,  Dr.  and  Mrs. 
H.  N.  McCoy,  Dr.  Julius  Meyer,  Dr.  E.  Moles,  Mr.  Julius  Nagy, 
Dr.  L.  C.  Newell,  Dr.  Gunnar  Nilson,  Dr.  R.  E  Oesper,  Mr.  E.  H. 
Parke,  Mr.  R.  B  Pilcher,  Mme.  J.  Presne,  Prof.  H.  Rheinboldt, 
Dr.  E.  H.  Riegel,  Senor  Pablo  Martinez  del  Rio,  Professor  Luigi 
Rolla,  Dr.  A.  S.  Russell,  Dr.  Stig  Ryden,  Dr.  E.  Segre,  Dr.  S.  E. 
Sheppard,  Dr.  H.  G.  Soderbaum,  Prof.  L.  von  Szathmary,  Dr.  W. 
T.  Taggart,  Dr.  L.  G.  Toraude,  Dr.  M.  W.  Travers,  Mr.  W.  D. 
Trow,  Miss  Amy  Wastf  elt,  and  Mr.  T.  A.  Wertime. 

Thoughtful  readers  and  reviewers  of  earlier  editions  of  this 
book  have  also  given  many  helpful  suggestions. 


MARY  ELVIRA  WEEKS 


Detroit 
May,  1956 


Contents 


Foreword      v 

1  Elements  known  to  the  ancient  world 3 

gold,  silver,  copper,  iron,  lead,  tin,  mercury,  sulfur, 
carbon 

2  Carbon  and  some  of  its  compounds 75 

3  Elements   of  the  alchemists 91 

arsenic,  antimony,  bismuth,  phosphorus 

4  More  on  the  discovery  of  phosphorus 121 

5  Some   eighteenth-century  metals 141 

zinc,  cobalt,  nickel,  manganese 

^6    Old  compounds  of  hydrogen  and  nitrogen 183 

7  Three  important  gases 197 

hydrogen,  nitrogen,  oxygen 

8  Rutherford,  discoverer  of  nitrogen 235 

9  Chromium,  molybdenum,  tungsten,  uranium 253 

10  Contributions  of  the  de  Elhuyar  brothers 285 

tungsten 

11  Tellurium  and  selenium 303 

12  Klaproth-Kitaibel  letters  on  tellurium 321 

13  Niobium  (columbium),  tantalum,  vanadium 339 

14  Contributions  of  Charles  Hatchett 369 

niobium 

15  Contributions  of  Andres  Manuel  del  Rio 391 

vanadium 

16  The  platinum  metals 407 

platinum,    rhodium,    osmium,    indium,    palladium, 
ruthenium 

17  Some  old  potassium  and  sodium  compounds 455 

ix 


X  CONTENTS 

18  Three  alkali  metals 473 

potassium,  sodium,  lithium 

19  J.  A.  Arfwedson  and  his  service  to  chemistry 495 

lithium 

20  Alkaline  earth  metals,  magnesium,  cadmium 505 

calcium,  barium,  strontium,  magnesium,  cadmium 

21  Elements  isolated  with  the  aid  of  potassium  and  sodium  .    .    .     543 

zirconium,  titanium,  cerium,  thorium 

22  Other  elements  isolated  with  the  aid  of  potassium  and  sodium    565 

beryllium,  boron,  silicon,  aluminum 

23  Some  spectroscopic  discoveries 619 

cesium,  rubidium,  thallium,  indium 

24  Periodic  system  of  the  elements 653 

25  Some  elements  predicted  by  Mendeleev 671 

gallium,  scandium,  germanium 

26  The  rare  earth  elements 695 

ytterbium,  cerium,  lanthanum,  neodymium,  praseo 
dymium,  erbium,  terbium,  yttrium,  scandium,  hol- 
mium,  thulium,  samarium,  gadolinium,  dysprosium, 
europium,  lutetium 

27  The  halogen  family 729 

fluorine.,  chlorine,  bromine,  iodine 

28  The  inert  gases 779 

helium,  neon,  argon,  krypton,  xenon 

29  The  natural  radioactive  elements 803 

radium,  polonium,  uranium,  radon,  protactinium, 
actinium,  thorium 

30  Discoveries  by  X-ray  spectrum  analysis 845 

hafnium,  rhenium 

31  Elements  discovered  by  atomic  bombardment 859 

francium,  technetium,  promethium,  astatine,  neptu 
nium,  plutonium,  americium,  curium,  berkelium, 
californium,  mendelevium,  einsteinium,  fermium 

List  of  the  chemical  elements 884 

Chronology  of  element  discovery 886 

Index 899 


Discovery 
of  the  Elements 


Hermes  Trismegistos 


The  world  of  chemical  reactions  is  like  a  stage,  on 
which  scene  after  scene  is  ceaselessly  played.  The 
actors  on  it  are  the  elements  (1). 

What  connection  do  the  books  show  between  the 
•fifty  or  sixty  chemical  elements  and  the  historical 
eras?  (119). 


Elements  known  to  the  ancient  world 


Although  the  ancient  conception  of  an  element  was  quite  different 
from  the  modern  one,  a  few  of  the  substances  now  recognized  as 
chemical  elements  have  been  known  and  used  since  the  dawn  of 
history.  Although  no  one  knows  who  discovered  these  ancient 
"building-stones  of  the  universe"  the  writings  of  Pliny  the  Elder 
and  Dioscorides  and  the  Hebrew  and  Hindu  Scriptures  abound 
in  interesting  allusions  to  the  metals,  gold,  silver,  copper,  iron, 
lead,  tin,  and  mercury,  and  the  non-metals,  sulfur  and  carbon. 

T 

JL  he  chemical  elements,  those  primeval  building  materials  from 
which  Nature  has  constructed  all  her  varied  forms,  have  been  discovered, 
one  by  one,  through  the  ages,  by  patient  searchers  in  many  lands.  The 
ancient  Greek  philosophers  Thales,  Xenophanes,  and  Heraclitus  believed 
that  all  substances  were  composed  of  a  single  element,  but  they  did  not 
agree  as  to  its  nature.  Thales  thought  that  water  was  the  element  which, 
upon  evaporating  and  condensing,  produced  all  substances.  Heraclitus, 
however,  believed  that  fire  was  the  one  fundamental  building  material. 

The  conception  of  four  simple  substances  (earth,  air,  water,  and  fire) 
had  its  origin  in  the  mind  of  Empedocles  about  four  hundred  and  forty 
years  before  the  birth  of  Christ,  and  held  sway  for  many  centuries.  Every 
one  knows  today  that  neither  earth  nor  air,  water  nor  fire  is  an  element. 
Earth  is  the  most  complex  of  all,  for  it  can  be  separated  into  many  chemical 
compounds,  whose  natures  vary  according  to  the  locality  from  which  the 
soil  has  been  taken.  From  air  can  be  obtained  a  number  of  simple  gases, 
among  them  nitrogen,  oxygen,  and  argon.  Water,  also,  can  be  easily 
decomposed  into  the  two  gaseous  elements,  oxygen  and  hydrogen;  and 
fire,  far  from  being  an  element,  consists  of  the  incandescent  gases  or  glow 
ing  embers  of  the  fuel  which  is  being  burned.  Simple  as  these  facts  may 
seem  to  the  modern  mind,  the  world's  best  intellects  once  debated  them 
and  established  them. 

During  the  centuries,  man's  conception  of  what  constitutes  a  chemi 
cal  element  has  undergone  many  other  changes.  Aristotle  ( 384-322  B.C. ) 
believed  that  the  properties  of  substances  are  the  result  of  the  simultane 
ous  presence  or  blending  of  certain  fundamental  properties  (102).  He 


DISCOVEKY  OF  THE  ELEMENTS 


spoke  o£  "elements"  only  in  the  sense  of  hypothetical  bearers  of  these 
fundamental  properties,  not  as  undecomposable  substances  that  can  be 
detected  empirically  and  isolated.  The  Aristotelian  doctrine  was  there 
fore  concerned  not  with  what  modern  chemists  call  elements  but  with 
an  abstract  conception  of  certain  properties,  especially  coldness,  hotness, 
dryness,  and  moistness,  which  may  be  united  in  four  combinations :  dry- 


From  Delbrueck's  "Antike  Portr tits'" 
Heraclitus,  540-475  B.C.    Ascetic  Greek  philosopher  and  founder  of  meta 
physics.     He  believed  that  fire  is  the  primary  substance,  and  that  change  is 
the  only  actuality  in  Nature. 

ness  and  heat  (fire),  heat  and  moisture  (air),  moisture  and  cold  (water), 
and  cold  and  dryness  (earth)  (102).  Aristotle  and  his  followers  believed 
that  all  substances  are  composed  of  these  four  elemental  states  of  matter. 

In  the  twelfth  century  there  appeared  in  certain  Latin  works  alleged 
to  be  translations  from  the  Arabic  the  theory  of  the  principles  of  metals: 
namely  mercury,  which  confers  metallic  properties,  and  sulfur,  which 
causes  the  loss  of  these  properties  on  roasting.  Another  principle,  salt, 
which  imparted  refractoriness  or  "fixity  in  the  fire,"  was  added  later  by 
the  famous  popularizer  of  medical  chemistry,  Paracelsus  (85). 

In  1661  Robert  Boyle  published  "The  Sceptical  ChymisC  a  book  in 
which  he  discussed  the  criteria  by  which  one  can  decide  whether  a  sub 
stance  is  or  is  not  a  chemical  element.  He  concluded  that  the  four 
Aristotelian  elements  and  three  principles  commonly  accepted  in  his  time 
cannot  be  real  chemical  elements  since  they  can  neither  compose  nor  be 


ELEMENTS  KNOWN  TO  THE  ANCIENTS  5 

extracted  from  substances  (85).  He  stated  clearly  "I  now  mean  by  Ele 
ments,  as  those  Chymists  that  speak  plainest  do  by  their  Principles,  certain 
Primitive  and  Simple,  or  perfectly  unmingled  bodies;  which  not  being 
made  up  of  any  other  bodies,  or  of  one  another,  are  the  Ingredients  of 
which  all  those  call'd  perfectly  mixt  Bodies  are  immediately,  compounded, 
and  into  which  they  are  ultimately  resolved:  now  whether  there  be  any 
one  such  body  to  be  constantly  met  with  in  all,  and  each,,  of  those  that 
are  said  to  be  Elemented  bodies,  is  the  thing  I  now  question"  ( 84 ) .  In 
spite  of  its  clearness,  this  definition  of  a  chemical  element  played  no  im 
portant  part  in  the  progress  of  chemistry  for  more  than  a  century. 

In  1789  A.-L.  Lavoisier  stated  in  his  "Traite  filementaire  de  Chimie": 
"If  ...  we  attach  to  the  name  of  element  or  principle  of  bodies  the  idea 
of  the  last  term  to  which  analysis  reaches,  then  all  substances  whicji  we 
have  not  yet  been  able  by  any  means  to  decompose  are  elements  to  us— 
not  that  we  can  be  sure  that  these  bodies  which  we  regard  as  simple  may 
not  themselves  be  composed  of  two  or  even  of  a  greater  number  of 
principles,  but  since  these  principles  are  never  separated,  or  rather,  since 
we  have  no  means  of  separating  them,  they  act  as  far  as  we  are  concerned 
in  the  manner  of  simple  bodies,  and  we  ought  not  to  suppose  them  com 
pounded  until  experience  and  observation  shall  have  furnished  the 
proof*  (84).  Even  since  Lavoisier's  time  however  the  concept  of  element 
has  undergone  many  changes.  In  his  list  of  elements,  for  example,  he  in 
cluded  light  and  heat  (caloric),  which  of  course  are  now  known  to  be 
forms  of  energy.  The  changing  views  concerning  the  definition  of  a 
chemical  element  have  been  set  forth  in  a  scholarly  manner  by  B.  N. 
Menschutkin  (82),  Tenney  L.  Davis  (84),  }.  R.  Partington  (85),  and 
Marie  Boas  (103,105). 

The  story  of  the  "defunct  elements,"  those  so-called  "elements"  which 
were  later  found  to  be  complex,  is  most  interesting,  but  the  present  narra 
tive  will  be  confined  to  the  simple  substances  now  recognized  by  chemists. 
The  curious  false  elements,  considerably  more  than  a  hundred  in  number, 
were  described  in  a  fascinating  article  by  Charles  Baskerville  (2). 

ANCIENT  METALS 

The  chemical  elements  which  were  undoubtedly  known  to  th£  ancient 
world  are  the  metals:  gold,  silver,  copper,  iron,  lead,  tin,  and  mercury, 
and  the  non-metals:  sulfur  and  carbon.  The  ancient  Jews,  as  one  learns 
from  the  Old  Testament,  were  certainly  acquainted  with  the  first  six. 

The  six  metals  mentioned  in  the  Bible  are  gold,  silver,  copper,  tin, 
lead,  and  iron.  Eleazar  the  priest  classified  them  all  as  substances  that 
can  be  purified  by  fire:  "the  gold,  and  the  silver,  the  brass,  the  iron,  the 


6  DISCOVEKY  OF  THE  ELEMENTS 

tin,  and  the  lead"  (Num.  31?  22).  The  word  brass  in  this  passage  means 
bronze,  an  alloy  of  copper  and  tin.  Isaiah's  vision  of  the  new  Jerusalem 
therefore  implies  knowledge  or  application  of  five  of  these  metals.  In  the 
Smith-Goodspeed  translation,  it  reads  as  follows: 

"Instead  of  bronze  will  7  bring  gold, 

And  instead  of  iron  will  I  bring  silver; 

And  instead  of  wood,  bronze, 

And  instead  of  stones,  iron; 

And  Peace  will  I  make  your  government, 

And  Righteousness  your  ruler"  (Isa.  60,  17)  (37) . 

The  same  metals  were  also  known  to  Daniel  (Dan.  2,  32-3;  5,  4).  The 
modern  Brazilian  Portuguese  translation,  however,  reads  copper  ( cobre ) 
instead  of  bronze  in  all  these  passages  (88). 

In  the  missing  portion  of  the  second  book  of  Esdras  which  the  British 
Orientalist  Robert  L.  Bensly  discovered  at  Amiens  and  published  in  1875, 
the  angel  says  (in  speaking  to  Ezra  of  the  earth),  "You  produce  gold  and 
silver  and  copper  and  also  iron  and  lead  and  clay.  But  silver  is  more 
abundant  than  gold,  and  copper  than  silver,  and  iron  than  copper,  lead 
than  iron,  and  clay  than  lead"  (II  Esdras  7,  55-6)  (37). 

The  ancient  Hindus  used  these  metals  also,  for  Sir  Praphulla  Chandra 
Ray  quotes  from  the  Charaka:  "Gold  and  the  five  metals  .  .  .  silver, 
copper,  lead,  tin,  and  iron"  (3).  R.  N.  Bhagvat  of  Bombay  published  in 
the  Journal  of  Chemical  Education  an  interesting  article  on  knowledge 
of  the  metals  in  ancient  India  and  illustrated  it  with  pictures  of  gold, 
silver,  copper,  and  iron  utensils;  an  iron  furnace;  the  famous  wrought 
iron  pillar  near  Delhi,  weighing  about  ten  tons  and  believed  to  date  from 
about  the  fourth  century  A.D.;  and  a  copper  blast  furnace  (87).  He 
believed  that  even  in  the  time  of  the  most  ancient  Vedas  (the  most  sacred 
writings  of  the  Hindus),  "metals,  including  iron,  were  well  known  and 
that  the  craft  of  metalworking  had  reached  a  fairly  advanced  stage"  (87). 
The  Vedic  period  extended  from  about  5000  to  4500  B.C. 

GOLD 

Gold  ornaments  have  been  found  in  Egyptian  tombs  of  the  prehistoric 
stone  age,  and  the  Egyptian  goldsmiths  of  the  earliest  dynasties  were 
skillful  artisans,  The  metal  was  used  as  a  medium  of  exchange  in  the  days 
of  Abraham,  and  is  mentioned  in  Exodus,  Deuteronomy,  the  First  Book  of 
Kings,  Job,  the  Psalms,  the  Proverbs,  Isaiah,  Lamentations,  Haggai,  and 
Zechariah  (4).  The  reference  in  Genesis  to  the  good  gold  of  Havilah 
(the  sand  land)  is  evidence  of  the  great  antiquity  of  this  metal  (Gen.  2, 
11-12).  Its  malleability  and  ductility  were  already  recognized  and 


ELEMENTS  KNOWN  TO  THE  ANCIENTS  7 

» 

utilized  when  Aaron's  vestments  were  embroidered:  "And  they  did  beat 
the  gold  into  thin  plates,  and  cut  it  into  wires,  to  work  it  in  the  blue,  and 
in  the  purple,  and  in  the  scarlet.,  and  in  the  fine  linen,  with  cunning  work" 
(Ex.  39,3). 

In  the  time  of  David  and  Solomon,  both  precious  and  useful  metals 
were  available  in  quantities.  In  charging  Solomon  to  build  the  Temple, 
David  said,  "Of  the  gold,  the  silver,  and  the  brass,  and  the  iron  there  is 
no  number"  (I  Chron.  22, 14,  16).  The  word  brass  in  this  passage  means 
bronze  (37).  Solomon's  fleet,  manned  by  his  servants  and  King  Hiram's 
experienced  Tyrian  sailors,  embarked  from  Ezion-Geber,  near  Eloth  in 
the  land  of  Edom  on  the  Red  Sea,  proceeded  to  Ophir,  and  returned  with 
four  hundred  and  twenty  talents  (more  than  twelve  million  dollars' 
worth)  of  gold  (I  Kings  9,  26-8).  Nelson  Glueck  believes  that  the  port 
city  of  Ezion-Geber  and  its  successor  Elath  (sic)  were  located  at  the 
north  end  of  the  Gulf  of  'Aqabah  in  the  Early  Iron  Age  (89). 

In  the  prophetic  book  of  Isaiah  (as  translated  by  Alex.  R.  Gordon) 
stands  the  promise: 

"I  shall  still  the  pride  of  the  arrogant, 

And  shall  bring  low  the  haughtiness  of  tyrants; 

I  shall  make  man  rarer  than  fine  gold, 

Mankind  more  rare  than  gold  of  Ophir"  (Isa.  13,  12)   (37). 

Gold  was  brought  from  Ophir,  Arabia,  Sheba,  and  (to  a  lesser  extent) 
from  Uphaz  (the  high  country)  and  Parvaim  (Jer.  10?  9;  II  Chron.  33  6; 
9,  1,  14).  When  Carsten  Niebuhr  traveled  through  Arabia  in  1761-63, 
he  stated  that  the  Greeks  and  Latins  had  often  mentioned  the  immense 
quantities  of  gold  produced  there.  He  said,  however,  "In  remote  times 
possibly,  when  the  Arabians  were  the  factors  of  the  trade  to  India,  much 
of  this  precious  metal  might  pass  through  Arabia  into  Europe;  but  that 
gold  was  probably  the  produce  of  the  mines  of  India.  At  present,  at  least, 
there  is  no  gold  mine  in  Arabia  .  .  ."  (90).  The  first  book  of  the 
Maccabees  mentions  the  silver  and  gold  mines  of  Spain  (I  Mace.  8,  1-3). 
The  metallurgical  parables  and  analogies,  like  the  agricultural  ones, 
express  some  of  the  loftiest  truths  in  the  Scriptures.  Metallurgical  proc 
esses  for  the  precious  metals  are  described  in  Malachi,  the  Psalms,  and 
the  Proverbs:  "But  who  may  abide  the  day  of  his  coming?  and  who  shall 
stand  when  he  appeareth?  for  he  is  like  a  refiner's  fire,  and  like  fullers' 
soap:  And  he  shall  sit  as  a  refiner  and  purifier  of  silver:  and  he  shall 
purify  the  sons  of  Levi,  and  purge  them  as  gold  and  silver,  that  they  may 
offer  unto  the  Lord  an  offering  in  righteousness"  (Mai.  3,  2-3).  "For 
thou,  O  God,  hast  proved  us:  thou  hast  tried  us,  as  silver  is  tried" 
(Ps.  66,  10).  "The  fining  pot  is  for  silver,  and  the  furnace  for  gold:  but 


8  DISCOVERY  OF  THE  ELEMENTS 

« 

the  Lord  trieth  the  hearts"  (Prov.  17,  3).  "As  the  fining  pot  for  silver 
and  the  furnace  for  gold;  so  is  a  man  to  his  praise"  (Prov.  27,  21) .  Alex. 
R.  Gordon  translates  this  as  "smelter"  instead  of  fining  pot  (37).  The 
modern  Spanish  and  Brazilian  Portuguese  translations,  however,  use  the 
word  "crisol"  or  crucible  (88,  91). 

The  art  of  working  gold  is  exceedingly  ancient.  The  two  leading 
goldsmiths  who  accompanied  Moses  through  the  wilderness  were  Bezaleel 
of  the  tribe  of  Judah  and  Aholiab  of  the  tribe  of  Dan,  who  were  highly 
skilled  in  metal-working  and  in  many  other  arts  (Ex.  31,  1-11;  35,  30-35; 
38,  22-3).  Moses  himself  was  doubtless  familiar  with  these  crafts,  for 
(according  to  Luke)  he  "was  learned  in  all  the  wisdom  of  the  Egyptians" 
(Acts  7,  22).  Isaiah  mentioned  the  goldsmith's  art  as  applied  to  the  con 
struction  of  idols:  "So  the  carpenter  encouraged  the  goldsmith.  .  .  . 
They  lavish  gold  out  of  the  bag,  and  weigh  silver  in  the  balance,  and  hire 
a  goldsmith;  and  he  maketh  it  a  god.  .  ."  (Isa.  41,  7;  46,  6). 

Pliny  the  Elder  (A.D.  23-79)  said  that  grains  of  gold  were  found 
in  the  stream-beds  of  the  Tagus  in  Spain,  the  Po  in  Italy,  the  Hebrus  in 
Thracia,  the  Pactolus  in  Asia  Minor,  and  the  Ganges  in  India  (5).  In 
the  second  century  before  Christ,  a  cupellation  process  was  used  for  re 
fining  the  metal,  and  in  Pliny's  time  the  mercury  process  was  well 
known  (6). 

Vitruvius,  who  lived  in  the  reign  of  Augustus,  mentioned  the  use 
of  mercury  to  recover  finely  divided  gold.  "When  gold  has  been  woven 
into  a  garment,"  said  he,  "and  the  garment  becomes  worn  out  with  age 
so  that  it  is  no  longer  respectable  to  use,  the  pieces  of  cloth  are  put  into 
earthern  pots,  and  burned  up  over  a  fire.  The  ashes  are  then  thrown 
into  water  and  quicksilver  added  thereto.  This  attracts  all  the  bits  of 
gold,  and  makes  them  combine  with  itself.  The  water  is  then  poured 
off,  and  emptied  into  a  cloth  and  squeezed  in  the  hands,  whereupon  the 
quicksilver,  being  a  liquid,  escapes  through  the  loose  texture  of  the  cloth, 
but  the  gold,  which  has  been  brought  together  by  the  squeezing,  is  found 
inside  in  a  pure  state"  (47). 

Paul  Bergs0e  of  Copenhagen  has  published  photographs  of  many 
small  golden  fishhooks,  forceps,  nails,  tacks,  pins,  sewing  needles,  spoons, 
trinkets,  and  ornaments  made  at  Esmeraldas  and  La  Tolita,  Ecuador,  by 
pre-Columbian  Indians  (106).  They  are  composed  of  gold  alloyed  with 
platinum  and  silver  in  varying  proportions. 

Archaeologists  have  found  that  the  province  of  Cocle  in  Panama  is 
rich  in  gold  artifacts  (117).  In  the  spring  of  1940  a  scientific  expedition 
from  the  University  of  Pennsylvania  excavated  a  pre-Columbian  ceme 
tery  in  this  province,  about  one  hundred  miles  west  of  Panama  City,  and 
brought  back  to  the  Museum  a  great  collection  of  large  repousse  plaques, 


ELEMENTS   KNOWN    TO   THE    ANCIENTS 


9 


a  four-inch  crocodile  with  a  one-inch  emerald  set  in  its  back,  pendants, 
nose  clips,  beads,  cuffs,  and  greaves,  all  of  nearly  pure  gold.  The  gold 
ornaments  found  on  one  chieftain  weighed  one  hundred  ounces  troy. 
The  area  from  which  these  objects  were  excavated  was  only  54  by  27 
feet. 

Even  on  his  first  voyage,  Christopher  Columbus  was  not  disappointed 
in  his  quest  for  gold.  In  a  letter  to  Luis  de  Santangel,  Chancellor  of  the 
Exchequer  of  Aragon,  he  wrote  on  February  15,  1493,  "Espanola  [Haiti] 
is  a  wonder.  .  .  .  The  harbours  on  the  coast  and  the  number  and  size 
and  wholesomeness  of  the  rivers,  most  of  them  bearing  gold,  surpass 
anything  that  would  be  believed  by  one  who  had  not  seen  them.  .  .  . 
In  this  island  there  are  many  spices  and  extensive  mines  of  gold  and 
other  metals.  The  inhabitants  have  neither  iron,  nor  steel,  nor  arms.  .  .  . 


Pliny  the  Elder,  23-79  A.D.  Roman 
philosopher.  Author  of  a  "Natural 
History"  in  37  books,  in  which  he 
discussed  the  astronomy,  geology, 
zoology,  botany,  agriculture,  miner 
alogy,  and  medicine  of  his  time. 


They  never  refuse  anything  that  they  possess  .  .  .;  on  the  contrary,  they 
offer  it  themselves,  and  they  exhibit  so  much  loving  kindness  that  they 
would  even  give  their  hearts.  ...  I  forbade  that  worthless  things.  .  . 
should  be  given  to  them"  (107). 

In  a  letter  describing  the  second  voyage,  Dr.  Chanca,  physician  to 
the  fleet  of  Columbus,  wrote  that  "the  Indians  beat  the  gold  into  very 
thin  plates,  in  order  to  make  masks  of  it.  ...  It  is  not  the  costliness  of 
the  gold  that  they  value  in  their  ornaments,  but  its  showy  appearance.  .  .  . 
It  appears  to  me  that  these  people  put  more  value  upon  copper  than 
gold'*  (107).  The  gold  mines  of  Cibao  in  the  interior  of  Haiti  [Hispan- 
iola]  were  discovered  by  Alonso  de  Ojeda  in  1494  (108). 


10  DISCOVERY  OF  THE  ELEMENTS 

On  his  fourth  voyage,  Columbus  wrote  in  1503  that  "in  this  land  of 
Veragua  [Panama]  I  saw  more  signs  of  gold  in  the  first  two  days  than  I 
saw  in  Espaiiola  [Haiti]  during  four  years"  (107). 

Gonzalo  Fernandez  de  Oviedo  y  Valdes,  "surveyor  of  the  melting 
shops  pertayning  to  the  gold  mynes  of  the  firme  Land"  [Tierra  Firma, 
Panama],  said  that  most  of  the  wrought  gold  of  the  Indians  was  con 
taminated  with  copper.  He  described  the  mining  procedure  in  detail, 
and  stated  that  the  Indian  women  were  highly  skilled  in  panning  gold 
(109).  "The  Indians,"  he  said,  "can  very  excellently  gild  such  Vessels  of 
Copper  and  base  Gold  as  they  make.  .  ."  (110). 

In  1534  Pedro  Sancho,  secretary  to  Governor  Francisco  Pizarro,  in 
his  report  of  the  conquest  of  Peru,  described  the  gold  and  silver  artifacts 
and  life-size  statues  found  in  Cuzco,  the  ancient  Inca  capital.  "Amongst 
other  things,"  said  he,  "there  were  sheepe  of  fine  gold  very  great,  and 
ten  or  twelve  statues  of  women  in  their  just  bignesse  and  proportion, 
artificially  composed  of  fine  Gold.  .  ."  (111). 

In  1586  Lopez  Vaz,  a  Portuguese,  told  Captain  Withrington  that 
"The  first  Land  that  is  inhabited  by  the  Spaniards  along  the  Coast  is 
called  Veragua  [Panama];  this  is  the  most  richest  Land  of  Gold  then  [sic] 
all  the  rest  of  the  Indies :  therefore  it  is  inhabited  with  Spaniards."  He 
added  that  the  Spaniards  endured  sickness  and  other  hardships  for  the 
sake  of  the  gold  which  they  obtained  from  the  rivers  with  Negro  labor 
(112). 

In  his  "Natural  and  Moral  History  of  the  Indies,"  which  was  first 
published  in  Seville  in  1590,  Father  Jose  de  Acosta  said  that  he  had  found 
aborigines  who  had  no  desire  to  possess  gold,  and  that  the  Indians,  in 
stead  of  using  gold,  silver,  or  any  other  metal  for  money,  bartered  their 
products  and  used  the  metals  only  for  ornament  (113).  Padre  de  Acosta 
also  stated  that  "it  is  wel  knowne  by  approved  histories  that  the  Yncas  of 
Peru  did  not  content  themselves  with  great  and  small  vessels  of  gold,  as 
pots,  cups,  goblets,  and  flagons  .  .  .  but  they  had  chaires  also  and  litters 
of  massie  golde,  and  in  their  temples  they  had  set  vppe  manie  Images  of 
pure  gold.  .  ."  (113). 

Padre  A.  A.  Barba  regarded  gold  as  "the  most  perfect  of  all  inanimate 
bodies  created  by  Nature."  He  stated  that  the  city  of  La  Paz  was  "fertile 
in  gold"  and  that  "during  the  rainy  season,  boys  find  Nuggets  in  the 
Streets,  especially  in  that  one  which  descends  by  the  Monastery  of  the 
Dominicans  towards  the  river"  (114).  Even  in  the  twentieth  century, 
these  ancient  gold  artifacts  are  sometimes  unearthed.  S.  K.  Lothrop  has 
told  in  American  Antiquity  how  some  Peruvian  boys  of  fifteen  years  and 
younger  found  a  golden  crown,  bracelets,  and  vases  at  the  bottom  of  a 
trench  formed  by  a  break  in  an  irrigation  ditch  at  Chongoyape  (115). 


ELEMENTS  KNOWN  TO  THE   ANCIENTS 


11 


In  the  autumn  of  1699  Dr.  James  Wallace  made  a  voyage  to  New 
Caledonia  in  Darien.  In  his  account  of  it  in  the  Philosophical  Trans 
actions  he  wrote:  "This  Country  certainly  affords  Gold  enough,  for  be 
sides  that  the  Natives  constantly  assure  us  that  they  Know  several  Gold- 
Mines  on  this  side;  besides  that,  I  say,  the  Plates  they  Wear  in  their 
Noses  and  the  Quantity  of  Gold  that  is  amongst  them  is  enough  to  per- 
swade  any  Man  of  the  Truth  of  it.  There  was  one  Night  aboard  here 
some  Indians  that  had  a  hundred  Ounces  of  Gold  about  them"  (116). 

Georgius  Agricola  used  the  touchstone  and  touch  needles  for  ex 
amining  bullion,  coins,  and  jewelry,  but  did  not  test  with  acid  the 


From  Biringuccio's  "Pirotechnia" 


An  Assay  Furnace,  1540 


"streak"  which  the  metal  left  on  the  black  siliceous  stone.  Other  time- 
honored  tests  for  gold  were  its  specific  gravity,  as  determined  by  Archi 
medes;  its  resistance  to  atmospheric  oxidation  on  fusion,  as  shown  in  the 
"trial  by  fire";  its  resistance  to  the  oxidizing  power  of  litharge  in  cupella- 
tion;  and  its  insolubility  in  acids.  By  the  early  sixteenth  century  some 
assayers  had  become  proficient  in  the  "parting"  of  gold  and  silver  (118). 

Although  assayers  were  usually  not  deceived  by  imitation  gold,  the 
"augmentation"  of  it  was  more  difficult  to  detect.  Since  gold  persistently 
retains  some  of  the  mercury  used  in  its  amalgamation,  absorbs  silver 
from  argentiferous  lead,  and  may  also  absorb  copper,  alchemists  were 
able  to  "augment"  the  weight  of  their  product  (118). 

Gold  Ruby  Glass.  The  ancient  Egyptians  were  masters  of  the  art  of 
adding  metallic  oxides  and  minerals  to  the  colorless  frit  to  produce  glass 


12  DISCOVERY  OF  THE  ELEMENTS 

of  various  colors.  In  their  most  ancient  red  glass,  the  color  was  usually 
produced  by  iron  or  copper.  Gold  ruby  glass  is  of  much  later  origin 
(120}.  In  his  Alchymia,  which  was  first  published  in  1595,  Andreas 
Liebau  ( Libavius )  told  how  to  use  gold  solutions  to  produce  a  red  color 
in  glass  and  thus  to  imitate  the  ruby  (120,  12,1,  122).  Father  Antonio 
Neri  and  Isaac  and  Johann  Isaac  Hollandus,  contemporaries  of  Libavius, 
prepared  ruby  glass  that  was  transparent  like  the  carbuncle  by  adding 
to  the  colorless  frit  a  powder  prepared  by  repeatedly  treating  gold  with 
a  mixture  of  nitric  and  hydrochloric  acids  (aqua  regia),  evaporating  to 
dryness,  and  heating  the  residue  in  a  small  reverberatory  furnace  until 
it  became  red  (120). 

In  the  seventeenth  century  J.  R.  Glauber  reduced  gold  solutions  with 
tin.  Although  the  resulting  precipitate  is  known  as  "purple  of  Cassius," 
Johann  Kunckel  stated  that  Dr.  Andreas  Cassius  may  have  learned  the 
secret  of  it  from  Glauber  (120,  121).  With  this  powder  Dr.  Cassius 
prepared  ruby  glass  by  a  process  which  Kunckel  afterward  developed 
to  a  high  stage  of  perfection.  In  his  "Vollstandiges  Laboratorium 
Chymicum/'  Kunckel  wrote:  "It  originated  in  the  following  manner. 
There  was  a  doctor  of  medicine  by  the  name  of  Cassius,  who  discovered 
the  Praecipitationem  Solis  cum  Jove  (precipitation  of  gold  with  tin),  to 
which  perhaps  Glauber  may  have  given  the  impulse,  on  which  I  offer 
no  opinion.  This  aforesaid  Dr.  Cassius  tried  to  introduce  it  into  glass; 
when,  however,  he  wanted  to  form  it  into  glass  or  when  it  came  out  of 
the  fire,  it  was  as  clear  as  any  other  crystal,  and  he  could  not  bring  it 
to  any  permanent  redness.  As  a  man  of  curiosity,  he  may,  however, 
have  noticed  among  the  glass-blowers  that  a  color  often  changes  through 
malaxation  [dilution]  in  the  flame  of  the  lamp,  wherefore  he  also  tried 
it,  and  thus  saw  the  handsomest  ruby  color.  When  I  learned  this, 
I  immediately  set  to  work,  but  how  much  trouble  I  had  to  discover 
the  composition  and  how  one  can  get  it  permanently  red,  I  myself  know 
best"  (120,  121,  123).  Some  fine  examples  of  Kunckel's  ruby  glass  still 
exist  (124). 

W.  P.  Jorissen  and  J.  Postma  have  shown  that  J.  R.  Glauber  described 
the  ruby  gold  in  1659,  a  quarter  of  a  century  before  Cassius  did  (125). 

Potable  Gold.  In  the  Kolloid-Zeitschrift,  H.  Losner  discussed  the 
history  of  colloidal  gold  and  quoted  several  early  recipes  for  the  prepa 
ration  of  red  gold  sols,  or  potable  gold  (Trinkgold).  Preparations  such 
as  this  were  made  by  Creiling  (1730),  Valentin  Krautermann  (1717), 
G.  E.  Stahl  (1744),  and  George  Wilson  (126). 

In  1746  William  Lewis  (1714-1781)  edited  George  Wilson's  "Corn- 
pleat  Course  of  Chymistry"  and  published  it  under  the  title  "A  Course 
of  Practical  Chemistry."  Wilson's  recipe  for  "Aurum  potabile,  as  I  pre- 


ELEMENTS  KNOWN  TO  THE  ANCIENTS  13 

pared  it  for  the  chief  physician  of  a  great  prince,  1692"  is  to  be  found 
in  that  volume  (127}.  His  earlier  researches  with  gold,  which  were 
begun  in  March,  1687,  ended  "the  eleventh  of  December;  when  I  was 
treated  as  the  Spanish  ambassador  was:  for  the  mob  taking  me  for  a 
conjurer,  or  something  worse,  broke  my  glasses  and  athanor;  saying  that 
I  was  preparing  the  devil's  fire-works,  purposely  to  burn  the  city  and 
Whitehall.  And  thus  ended  this  operation"  (127). 

Wilson's  contemporary  Nicolas  Lemery,  however,  more  distrustful 
of  alchemists,  said  that  "their  Aurum  potabile,  which  they  crack  with  so 
loud,  and  which  they  sell  at  so  dear  a  price,  is  commonly  nothing  else  but 
a  tincture  of  some  Vegetable  or  Mineral  whose  color  comes  near  to  that 
of  gold.  .  .  .  This  same  cheat  of  theirs  is  none  of  the  least  that  they 
use  to  get  by,  for  in  point  of  Medicins,  abundance  of  people  prove  extreme 
credulous  ..."  (128).  Geoffroy  the  Elder  concluded  "that  the  most 
valuable  and  most  precious  of  all  Metals  is  the  most  useless  in  Physick, 
except  when  considered  as  an  Antidote  to  Poverty"  (129). 

The  California  Gold  Rush.  Vague  references  to  an  Eldorado  on  an 
island  in  the  Pacific  appeared  as  early  as  the  sixteenth  century  (130). 
Early  in  1848  gold  was  found  at  Sutter's  mill  near  the  present  town  of 
Coloma,  California.  Among  the  claimants  to  the  honor  of  this  discovery 
may  be  mentioned  Captain  Charles  Bennett,  James  W.  Marshall  (his 
partner),  and  Emma  Bonney.  By  the  autumn  of  1848  incredible  reports 
had  gradually  circulated  in  the  United  States  that  the  inhabitants  of  the 
California  Territory,  but  lately  acquired  from  Mexico,  were  leaving  their 
customary  occupations  to  pan  gold.  Verification  of  these  reports  led  to 
the  great  "gold  rush  of  ?49,"  in  which  adventurous  men  from  all  walks  of 
life  made  the  tedious  and  perilous  journey  to  California  by  overland  trail, 
around  Cape  Horn,  or  across  the  disease-ridden  Isthmus  of  Panama 
(130,131,277). 

In  1859  a  party  of  miners  detected  gold  in  Dry  Creek,  near  Denver, 
Colorado.  Before  the  close  of  that  year,  the  gulches  near  Central  City 
were  swarming  with  gold  seekers  (132). 

Gold  in  Sea  Water.  Although  the  presence  of  gold  in  sea  water  has 
often  been  reported,-  Georges  Claude  estimated  the  gold  content  of  sea 
water  off  the  California  coast  (where  one  might  expect  it  to  be  above  the 
average  concentration  for  the  ocean  as  a  whole)  to  be  less  than  0.1 
milligram  per  cubic  meter  (133).  Gold  has  been  electroplated  from  sea 
water,  but  at  a  cost  five  times  the  value  of  the  metal.  Dr.  Colin  G.  Fink 
found  that  when  a  stationary  cathode  is  used,  the  gold  precipitates  out 
rapidly  in  colloidal  form.  With  a  rapidly  rotating  cathode,  it  is  possible 
to  get  a  visible  deposit  of  crystalline  gold  (134 ) . 


14  DISCOVERY  OF  THE  ELEMENTS 

SILVER 

Silver,  since  it  rarely  occurs  uncombined,  did  not  come  into  use  as 
early  as  did  gold  (29}.  In  Egypt  between  the  thirtieth  and  fifteenth 
centuries  before  Christ,  it  was  rarer  and  more  costly  than  gold.  It  must 
have  been  used  as  a  medium  of  exchange  long  before  it  was  coined,  for 
it  is  related  in  Genesis  that  when  Abraham  purchased  a  burial  place  for 
Sarah  he  weighed  out  the  silver  in  the  presence  of  witnesses  (7). 
Jeremiah,  too,  weighed  out  the  silver  when  he  purchased  the  family 
inheritance,  Hanameers  field  (Jer.  32,  9-10). 

In  the  ancient  cupellation  process  of  refining  gold  and  silver,  the 
impure  metal  was  heated  in  a  cupel  (a  shallow,  porous  cup  of  bone  ash) 
by  means  of  a  blast  of  air.  The  base  metals,  such  as  lead,  tin,  iron,  and 
copper,  were  thus  oxidized  and  absorbed  into  the  porous  cupel,  leaving 
a  button  of  unoxidizable,  noble  metal  behind.  Unless  lead  was  already 
present  as  an  impurity,  it  was  added  before  the  cupel  was  heated.  About 
seven  and  a  half  centuries  before  the  birth  of  Christ,  Isaiah  referred  to 
this  process  as  follows :  "And  I  will  turn  my  hand  upon  thee,  and  purely 
purge  away  thy  dross,  and  take  away  all  thy  tin"  (Isa.  L,  25).  The 
modern  Brazilian  Portuguese  translation  of  this  verse  reads:  "voltarei  a 
minha  mao  sobre  ti,  e  purificarei  como  com  potassa  a  tua  escoria,  e 
tirarei  de  ti  todo  o  teu  estanho"  ( 88 ) . 

A  century  and  a  half  later,  Jeremiah  described  the  cupellation  process 
more  vividly  in  his  rebuke  to  backsliding  Judah.  Although  the  metallur 
gical  meaning  is  evident  in  the  Authorized  Version,  it  is  brought  out 
still  more  clearly  in  the  translation  by  Alex.  R.  Gordon: 

"I  have  made  you  an  assayer  and  tester  among  my  people, 

That  you  may  prove  and  assay  their  ways. 

For  they  are  all  of  them  hardened  rebels, 

Dealers  in  slander; 

They  are  all  of  them  bronze  and  iron, 

Wholly  corrupt. 

The  bellows  are  scorched  with  the  fire, 

The  lead  is  consumed; 

But  in  vain  does  the  smelter  keep  on  smelting, 

The  dross  is  not  drawn  out. 

'Refuse  silver,*  are  they  called, 

For  the  Lord  has  refused  them"  (Jer.  6,  27-30)  (37) . 

The  modern  Spanish  translation  interprets  the  29th  verse  differently, 
however:  "Los  fuelles  soplan  furiosamente;  de  su  fuego  resulta  plomo 
.  .  .  (The  bellows  blow  furiously;  from  their  fire,  lead  results  .  .  ."), 
(91). 


ELEMENTS  KNOWN   TO  THE   ANCIENTS 


15 


Jeremiah  also  mentioned  sheet  silver.  For  the  embellishment  of  an 
idol,  "Silver  spread  into  plates  is  brought  from  Tarshish,  and  gold  from 
Uphaz,  the  work  of  the  workman,  and  of  the  hands  of  the  founder:  blue 
and  purple  is  their  clothing:  they  are  all  the  work  of  cunning  men'7 
(Jer.  10,  9).  The  Smith-Goodspeed  translation  refers  to  these  metals  as 
beaten  silver  from  Tarshish"  and  "gold  from  Ophir"  (37). 

In  the  parable  of  the  dross  in  the  furnace,  Ezekiel  described  the 
cupellation  process  in  detail:  "And  the  word  of  the  Lord  came  unto  me, 


Iron 


Silver 


Seventeenth-century  Symbols,  from  Peters's  "Aus  pharmazeutischer  Vorzeit 

in  Bild  und  Wort" 


saying,  Son  of  man,  the  house  of  Israel  is  to  me  become  dross:  all  they 
are  brass,  and  tin,  and  iron,  and  lead,  in  the  midst  of  the  furnace;  they 
are  even  the  dross  of  silver.  Therefore  thus  saith  the  Lord  God;  Because 
ye  are  all  become  dross,  behold,  therefore  I  will  gather  you  into  the  midst 
of  Jersusalem,  As  they  gather  silver,  and  brass,  and  iron,  and  lead,  and 
tin,  into  the  midst  of  the  furnace,  to  blow  the  fire  upon  it,  to  melt  it; 


16  DISCOVERY  OF  THE  ELEMENTS 

so  will  I  gather  you  in  mine  anger  and  in  my  fury,  and  I  will  leave  you 
there,  and  melt  you.     .    .    ."    Ezek.  22,  17-22. 

Zechariah,  too,  used  a  metallurgical  analogy  to  portray  the  saving 
of  a  remnant  of  the  people  in  Jerusalem:  "And  it  shall  come  to  pass, 
that  in  all  the  land,  saith  the  Lord,  two  parts  therein  shall  be  cut  off  and 
die;  but  the  third  shall  be  left  therein.  And  I  will  bring  the  third  part 
through  the  fire,  and  will  refine  them  as  silver  is  refined,  and  will  try 
them  as  gold  is  tried:  they  shall  call  on  my  name,  and  I  will  hear  them: 
I  will  say,  It  is  my  people:  and  they  shall  say,  The  Lord  is  my  God" 
(Zech.  13,  8-9).  The  metallurgical  analogies  in  the  Bible  were  thor 
oughly  discussed  and  explained  by  James  Napier  (1810-1884),  a  Scottish 
dyer  and  chemist  who  studied  under  Thomas  Graham  at  Glasgow  in  the 
same  class  with  David  Livingstone  (92,  93). 

In  the  New  Testament,  too,  silver  plays  an  important  role. 

When  Paul's  teaching  of  Christ's  gospel  endangered  the  livelihood 
of  Demetrius  and  other  silversmiths  who  made  and  sold  shrines  for  Diana 
at  Ephesus,  they  stirred  up  great  commotion  among  their  fellow  citizens 
(Acts  19,  23-41).  In  Paul's  time,  the  Ephesians  worshipped  Diana  and 
"an  image  which  fell  down  from  Jupiter."  The  latter  may  have  been  a 
meteorite.  Among  the  alchemists,  the  name  and  figure  of  Diana  long 
served  as  the  chemical  symbol  for  silver.  According  to  J.  R.  Partington, 
"Egyptian  silver  .  .  .  was  an  alloy  with  gold  containing  approximately 
60  to  92  per  cent  of  silver  and  3  to  38  of  gold,  with  occasionally  a  little 
copper,  and  was  probably  a  white  natural  product,  not  obtained  by 
smelting  an  ore."  He  also  stated  that  the  Greeks  first  worked  argentiferous 
galena  for  silver  in  about  the  seventh  century  B.C.  (135). 

Jagnaux  stated  that  when  the  Phoenicians  made  their  first  voyage  to 
Spain  they  found  more  silver  than  their  ships  could  carry,  and  that,  for 
this  reason,  they  weighted  their  wooden  anchors  with  silver  instead  of 
lead  (8).  When  the  Spaniards  conquered  Peru  they  found  many  silver 
utensils  that  had  been  made  by  the  ancient  inhabitants  (9,  28). 

Some  Ancient  Silver  Mines.  The  gold  and  silver  mines  of  Spain 
are  mentioned  in  the  Apocrypha.  In  the  days  of  the  Maccabees  they 
were  in  possession  of  the  Romans:  "Now  Judas  had  heard  of  the  fame 
of  the  Romans.  ...  It  was  told  him  also  of  their  wars  .  .  .  and  what 
they  had  done  in  the  Country  of  Spain,  for  the  winning  of  the  mines  of 
the  silver  and  gold  which  is  there  ..."  (136). 

In  1700  J.-P.  de  Tournefort  visited  the  Island  of  Kimolos  in  the 
Aegean  Sea.  "This  Island,"  said  he,  "by  the  Greeks  oalTd  Chimoli,  took 
the  name  of  Argentiere  at  the  time  when  the  Silver  Mines  were  first 
discover'd  there:  there  are  still  to  be  seen  the  Work-houses  and  Furnaces 
where  they  used  to  prepare  this  Metal"  (137). 


ELEMENTS   KNOWN  TO  THE   ANCIENTS  17 

In  the  first  edition  of  the  "Natural  History  of  the  West  Indies,"  which 
Gonzalo  Fernandez  de  Oviedo  y  Valdes  wrote  for  Charles  V.  in  1525,  he 
stated  that  Stephen  Gomez  had  recently  found  silver  and  copper  in 
northern  America  (108).  Oviedo  later  published  a  more  comprehensive 
work  on  the  same  subject  (109). 

The  silver  mines  of  Charcas,  Peru,  were  discovered  in  1535,  those  of 
Potosi,  Peru  (now  part  of  Bolivia),  in  1545,  those  of  Zacatecas,  Mexico, 
in  1548,  and  those  of  Guanajuato,  Mexico,  in  1550  (108).  The  first  coins 
struck  in  America  were  produced  in  Mexico  in  1536  under  the  viceroy- 
ship  of  Antonio  de  Mendoza.  They  were  of  copper  and  silver  (108). 

In  his  "Natural  and  Moral  History  of  the  Indies,"  Father  Jose  de 
Acosta  wrote  in  1590:  "The  Creator  hath  furnished  the  West  Indies  with 
so  great  a  treasure  of  silver,  as  all  that  which  we  reade  of  in  antient 
Histories  and  that  which  is  spoken  of  the  mines  of  Spaine,  and  other 
provinces,  is  not  comparable  to  that  we  see  in  those  partes.  . . .  The  maner 
to  purge  and  refine  siluer  [sic]  which  the  Indians  have  vsed  was  by  melt 
ing,  in  dissolving  this  masse  of  mettall  by  fire,  which  casts  the  earthly 
drosse  aparte,  and  by  his  force  separates  silver  from  lead,  tinne  from 
copper,  and  other  mettalls  mixt. 

"To  this  end,"  continued  Father  de  Acosta,  "they  did  build  small 
furnaces  in  places  whereas  the  wind  did  commonly  blow,  and  with  wood 
and  cole  made  their  refining,  the  which?  furnaces  in  Peru  they  call 
huayras.  Since  the  Spaniards  entred,  besides  this  manner  of  refining 
which  they  vse  to  this  day,  they  likewise  refine  silver  with  qvick-silver, 
and  draw  more  by  this  means  then  [sic]  in  refining  it  by  fire.  For  there 
is  some  kind  of  silver  mettal  found  which  can  by  no  means  be  purged 
and  refined  by  fire,  but  onely  with  quicksilver  .  .  ."  (45). 

According  to  Father  de  Acosta,  "the  chief  places  of  the  Indies  from 
which  they  draw  silver  are  New  Spaine  [Mexico]  and  Peru;  but  the 
mines  of  Peru  farre  surpasse  the  rest;  and  amongst  all  others  of  the 
worlde,  those  of  Potosi  [now  in  Bolivia]"  (45). 

Father  de  Acosta  then  went  on  to  tell  how  the  mines  of  Potosi  were 
discovered,  twelve  years  after  the  Spanish  conquest  of  Peru,  by  an 
Indian  named  Hualpa  of  the  province  of  Cuzco.  One  day  when  Hualpa 
was  hunting  deer,  he  had  to  take  hold  of  a  branch  in  order  to  climb  up  a 
rough  slope.  In  the  hole  left  by  the  uprooted  shrub,  Hualpa  saw  some 
metal.  After  it  had  been  assayed  at  Porco,  he  worked  the  rich  vein 
secretly  for  about  two  months  until  another  Indian,  named  Huanca,  dis 
covered  his  secret  (45).  Hualpa  then  gave  Huanca  another  vein  which 
was  equally  rich  in  silver  but  somewhat  more  difficult  to  work  than  the 
original  Diego  Centeno  vein.  Dissatisfied  with  this  agreement,  Huanca 
revealed  the  secret  to  his  Spanish  master,  Villarroel.  Thus  on  April  21, 


18  DISCOVERY  OF  THE  ELEMENTS 

1545,  Huanca  and  Villarroel  became  joint  owners  of  the  mines  of  Potosi, 
The  King  of  Spain  claimed  one-fifth  of  their  proceeds  (45). 

At  this  day,"  said  Father  de  Acosta,  "the  most  vsuall  maner  of 
refining  in  Potosi  is  by  quickesilver,  as  also  in  the  mines  of  Zacatecas,  and 
others  of  New  Spaine.  There  were  in  old  time,  vpon  the  sides  and  toppes 
of  Potosi,  above  six  thousand  Huayras,  which  are  small  furnaces  where 
they  melt  their  mettall,  the  which  were  placed  like  lights  (a  pleasant 
sight  to  behold  by  night)  casting  a  light  a  farre  off  like  a  flame  of 
fire.  .  .  .  But  at  this  day  there  are  not  above  two  thousand  .  .  ."  (45). 

In  1569  the  poet  Alonso  de  Ercilla  y  Zuniga  described  this  ancient 
process  and  the  hill  of  Potosi  in  his  poem  Araucana: 

"Pues  de  un  quintal  de  tierra  de  la  mina 
Las  dos  arrobas  son  de  plata  fina"  (113), 

which  may  be  translated: 

"For  from  one  quintal  of  earth  of  the  mine 
Two  arrobas  are  yielded  of  silver  fine" 

Of  the  assay  masters,  Father  de  Acosta  said,  "Their  ballaunce  and 
weights  are  so  delicate,  and  their  graines  so  small,  as  they  cannot  take 
them  vppe  with  the  hand,  but  with  a  small  paire  of  pincers:  and  this 
triall  they  make  by  candle  light,  that  no  ayre  might  moove  the  ballance. 
For  of  this  little  the  price  of  the  whole  barre  dependeth"  (45). 

In  the  seventeenth  century,  Father  Alvaro  Alonso  Barba  of  Potosi 
said  that  some  of  the  mines  there  had  been  worked  by  the  Incas  and  that, 
since  the  coming  of  the  Spaniards,  the  wealth  of  this  hill  had  been 
distributed  to  all  parts  of  the  world  (46). 

Silver  Trees.  In  the  eighteenth  century,  silver  solutions  were  re 
duced  in  various  ways  to  form  "the  tree  of  Diana,"  which  Erasmus  Darwin 
described  as  follows: 

"So  the  learn  d  Alchemist  exulting  sees 

Rise  in  his  bright  matrass  Diana's  trees; 

Drop  after  drop,  with  just  delay.,  he  pours 

The  red-fumed  acid  on  Potosi' s  ores; 

With  sudden  flash  the  fierce  bullitions  rise, 

And  wide  in  air  the  gas  phlogistic  flies; 

Slow  shoot,  at  length,  in  many  a  brilliant  mass 

Metallic  roots  across  the  netted  glass; 

Branch  after  branch  extend  their  silver  stems, 

End  into  gold,  and  blossoms  into  gems"  (138). 

De  la  Condamine  and  Wilhelm  Homberg  each  gave  methods  of  mak 
ing  so-called  vegetations  of  silver  and  other  metals  (139,  140),  Accord- 


ELEMENTS  KNOWN   TO   THE  ANCIENTS  19 

ing  to  Caspar  Neumann,  "If  solution  of  Silver  be  diluted  with  pure  water, 
a  considerable  quantity  of  pure  Mercury  added,  and  the  whole  set  in  a 
cold  place,  there  will  form  by  degrees  a  precipitation  and  crystallization 
resembling  a  little  tree,  with  its  root,  trunk,  and  branches,  called  Arbor 
Diarize,  or  the  philosophic  Silver-tree.  Lemery  gives  another  method  of 
making  an  Arbor  Dianse,  by  adding  to  solution  of  Silver  some  warm 
distilled  Vinegar"  (141).  Dr.  Neumann  also  described  the  formation  of 
a  silver  tree  by  spreading  silver  solution  on  a  glass  plate  and  placing  in 
the  center  of  it  a  piece  of  iron  or  other  metal  capable  of  precipitating 
silver.  He  added  that  solutions  of  other  metals  also  form  so-called 
vegetations,  "but  none  so  elegant  ones  as  that  of  Silver"  (141). 

COPPER 

Copper,  in  the  opinion  of  Berthelot,  has  been,  mined  for  at  least  five 
thousand  years.  He  found  by  analysis  that  the  most  ancient  Egyptian 
articles  were  made  of  pure  copper  rather  than  of  its  alloys  (10),  (27). 

The  word  copper  appears  in  the  Old  Testament  only  in  the  passage 
where  Ezra  describes  the  treasure  which  he  weighed  out  and  committed 
to  the  twelve  priests.  Besides  the  silver  and  gold  were  "two  vessels  of 
fine  copper,  precious  as  gold"  (11).  Leroy  Waterman,  however,  inter 
prets  this  word  as  "fine  burnished  bronze"  (37)  The  modern  Spanish 
and  Brazilian  Portuguese  translations  also  render  it  as  bronze  (88,  91). 

The  trade  of  coppersmith  is  mentioned  in  Isaias  41,  6-7  of  Bishop 
Challoner's  revision  of  the  Douai-Reims  Bible,  which  is  based  on  the 
Latin  Vulgate  (94).  The  corresponding  passage  in  the  Authorized  Ver 
sion  is  rendered  "goldsmith"  instead  of  "coppersmith"  (Isa.  41,  6-7).  In 
his  second  letter  to  Timothy,  Paul  mentioned  that  "Alexander  the  copper 
smith  did  me  much  evil"  (II  Tim.  4,  14).  Edgar  J.  Goodspeed  translates 
this,  however,  as  "metal-worker"  rather  than  coppersmith.  The  widow's 
mites  were  probably  small  copper  coins  (Mark  12,  43;  Luke  21,  2)  (37). 

The  word  "brass"  of  tJtie  Authorized  Version  of  the  Old  Testament 
sometimes  means  copper  and  sometimes  bronze.  The  passage  in  which 
Moses  describes  the  Promised  Land  as  "a  land  whose  stones  are  iron,  and 
out  of  whose  hills  thou  mayest  dig  brass"  is  evidently  an  allusion  to 
copper,  which  frequently  occurs  in  the  uncombined  state  (Deut  83  9). 
In  the  American  translation  by  J.  M.  Powis  Smith  and  Edgar  J.  Goodspeed 
and  in  the  modern  Brazilian  Portuguese  and  Spanish  translations,  it  is  so 
interpreted  (37,  88,  91).  This  description  would  hold  good  for  the 
Lebanon  or  for  the  Sinaitic  region  (95).  Rabbi  Joseph  Schwarz  wrote 
in  1845  that  "Except  in  the  neighbourhood  of  Aleppo,  no  Copper  is 
found  anywhere  in  Palestine.  I  was,  however,  told  that  Northern  Galilee 


J.  B.  ScoZtn,  sculp. 

Frontispiece   to    1733   French   Edition   of  Barba's   "Art   of   the   Metals/' 

The  poem  mentions  that  France  used  to  be  rich  in  precious  metals,  and 
questions  the  necessity  of  searching  for  them  in  the  New  World. 

Pourquoi  de  I'Ocean  courir  les  vastes  bords. 

France,  ne  trouvez  vo.*  de  TOr  quau  nouveau  Monde. 

En  Metaux  precieux  autrefois  si  feconde 

N'avez  vou$  pas  toujours  vos  immenses  Tresors. 


ELEMENTS  KNOWN  TO  THE   ANCIENTS  21 

and  the  lower  range  of  Lebanon  contain  veins  of  Copper"  and  that  this 
metal  was  also  obtained  on  the  Egyptian  frontier  (96). 

In  1934  a  joint  expedition  of  the  American  School  of  Oriental  Research, 
Baghdad,  the  Hebrew  Union  College,  the  American  Council  of  Learned 
Societies,  and  the  Transjordan  Department  of  Antiquities  made  a  thorough 
archaeological  survey  of  Edom.  Nelson  Glueck  and  his  fellow-explorers 
found  copper  slag-piles  and  ruins  of  ancient  smelting  furnaces  at  Kh. 
(Khirbet)  el-Gheweibeh,  Kh.  el-Jariyeh,  and  Kh.  Nqeib  Aseimer,  a 
great  mass  of  highly  cupriferous  sandstone  at  the  Wadi  el-Jariyeh;  and 
a  great  copper  mine  at  Umm  el-'Amad  (89).  On  the  surface  at  Kh. 
Jariyeh,  at  Mene'iyyeh,  and  at  Kh.  Nqeib  Aseimer,  they  found  good  ore 
of  mixed  cuprite  and  malachite. 

Since  the  region  is  poor  in  fuel,  the  furnaces  may  have  been  fired 
with  large  quantities  of  dried  shrubs,  a  fuel  still  used  in  Palestine  and 
Transjordan  for  firing  crude  lime  kilns  (89).  However,  since  immense 
quantities  of  copper  were  smelted  in  the  'Arabah  (the  fissure  extending 
for  about  185  kilometers  between  the  Dead  Sea  and  the  Gulf  of  'Aqabah) 
in  the  Early  Iron  Age,  much  of  the  fuel  must  have  been  brought  in  the 
form  of  charcoal  by  caravans  of  camels  and  donkeys  from  the  forests  of 
Edom  (89).  Long  before  the  coming  of  the  Israelites,  the  Kenites  and 
Edomites  worked  the  ore  deposits  of  the  'Arabah  (89).  The  archaeolog 
ical  evidence  shows  that  this  was  truly  "a  land  whose  stones  contain  iron, 
and  out  of  whose  hills  you  can  dig  copper"  (Deut  8,  9)  (37,  89). 

Dr.  Glueck  believes  that  Solomon's  fleet  which  used  to  sail  from 
Ezion-Geber  to  Ophir  once  every  three  years  for  gold,  silver,  ivory,  apes, 
and  peacocks  must  have  carried  as  export  cargo  copper  from  the  "Arabah 
(89).  He  believes  that  the  passage  should  read  "Tarshish  ships"  (going 
to  Ophir)  instead  of  "ships  sailing  to  Tarshish."  Since  both  water  and 
fuel  are  scarce,  the  countries  of  the  Near  East  found  it  cheaper  to  import 
their  copper  than  to  work  these  ancient  deposits  (89). 

In  1934  Rabbi  Glueck  excavated  a  site  a  few  miles  south  of  the 
Dead  Sea  and  discovered  King  Solomon's  copper  mines.  Four  years  later 
he  excavated  a  site  near  the  Gulf  of  'Aqabah  (the  Ezion-Geber  of  the 
Bible)  and  discovered  an  ancient  copper  mine  that  is  now  being  worked 
by  Israeli  miners  (267,  279).  Copper  mining  and  smelting  sites  have  also 
been  found  in  Sinai  ( 89 ) . 

Job's  statement  that  "brass  is  molten  out  of  the  stone"  must  refer  to 
the  smelting  of  copper  from  its  ore  ( Job  28,  2) .  Similarly,  the  two  "moun 
tains  of  brass"  which  Zechariah  described  in  the  vision  of  the  four  chariots 
must  have  been  mountains  of  copper  or  its  ore  (Zech.  6,  1)  (37). 

Although  the  Israelites  must  have  imported  their  copper,  the  Egyp 
tians  mined  this  jmetaj  even  before  the  time  of  Cheops  who  built  the  great 


22  DISCOVERY  OF  THE  ELEMENTS 

pyramid  at  Gizeh  ( 97) .  The  "isles  of  Chittim"  probably  included  Cyprus, 
famous  for  its  copper  mines.  "Javan>  Tubal,  and  Meshech,"  said  Ezekiel, 
"they  were  thy  merchants;  they  traded  the  persons  of  men  and  vessels  of 
brass  in  thy  market"  (Ezek.  27,  6,  13).  Long  before  the  Roman  period, 
copper  ore  and  ingots  were  exported  from  Cyprus,  and  its  mines  still  yield 
a  limited  amount  of  the  metal  (98).  The  inhabitants  of  New  Paphos 
(Old  Baffa)  on  this  island  worshipped  Venus  (99).  Among  the  alche 
mists,  Venus  symbolized  copper.  Copper  is  found  in  the  free  state  in 
Egypt,  the  Lake  Superior  region  of  North  America,  and  in  many  other 
parts  of  the  world,  and  can  be  obtained  from  malachite  ore  by  a  simple 
process.  Knives,  axes,  spear  heads,  chisels,  and  bracelets  of  this  metal  have 
been  found  in  Indian  mounds  in  Wisconsin,  Illinois,  and  neighboring 
states.  Indian  tools  and  excavations  for  working  the  copper  veins  have 
been  discovered  in  the  Ontonagon  region  of  northern  Michigan  (39). 
Much  of  the  copper  worked  by  the  aborigines  came  from  Isle  Royale  in 
Lake  Superior  (40). 

The  pre-Columbian  Indians  of  La  Tolita  on  the  Esmeraldas  coast  of 
Ecuador  made  small  axes,  bells,  sewing  needles,  and  filigree  work  by 
hot-hammering  native  copper.  Paul  Bergs0e  of  Copenhagen  has  made  a 
thorough  study  of  the  gold,  platinum,  and  copper  artifacts  of  this  region 
(41). 

Christopher  Columbus  wrote  in  1503,  on  his  fourth  voyage  to  the 
West  Indies,  "Some  of  the  people  whom  I  discovered  were  cannibals. 
.  .  .  They  say  that  there  are  great  mines  of  copper  in  the  country,  of 
which  they  make  hatchets  and  other  elaborate  articles,  both  cast  and 
soldered;  they  also  make  of  it  forges,  with  all  the  apparatus  of  the  gold 
smith,  and  crucibles"  (107). 

Stephen  Gomez,  in  his  journey  down  the  Atlantic  coast  from  Nova 
Scotia  to  Florida  in  1525,  found  copper  and  silver  in  the  north.  In  the 
following  year  Gonzalo  Fernandez  de  Oviedo  y  Valdes  (1478-1557) 
mentioned  Gomez  and  his  discoveries  in  his  work  on  the  natural  history 
of  the  New  World  (108). 

Coronado,  too,  saw  some  primitive  copper  artifacts.  Arriving  at  last 
in  the  fabled  Quivira  (now  part  of  Kansas)  after  his  remarkable  journey 
from  Compostela,  Mexico,  in  search  of  the  gold  and  silver  treasures 
described  by  his  false  guide  "the  Turk,"  Don  Francisco  Vazquez  de 
Coronado  wrote  King  Charles  V  on  October  20,  1541,  that  "the  natives 
there  gave  me  a  piece  of  copper  that  an  Indian  chief  wore  suspended 
from  his  neck.  I  am  sending  it  to  the  viceroy  of  New  Spain,  for  I  have 
not  seen  any  other  metal  in  this  region  except  this  and  some  copper  jingle 
bells  which  I  am  forwarding  to  him"  (42) .  In  his  treatise  on  the  Coronado 
expedition,  George  Parker  Winship  stated  that  Indian  traders  used  to 


ELEMENTS  KNOWN  TO  THE  ANCIENTS  23 

carry  pieces  of  copper  from  the  mines  on  the  shores  of  Lake  Superior, 
from  tribe  to  tribe,  as  far  east  as  the  Atlantic  Ocean  and  as  far  west  as 
the  Rocky  Mountains  ( 43 ) . 

In  describing  his  voyage  to  northern  Virginia  with  Sir  Walter 
Raleigh,  John  Brereton  wrote  in  1602  that  he  had  seen  Indians  wearing 
elaborate  chains,  earrings,  and  collars  of  copper,  and  that  some  o£  their 
arrow  heads  and  skull-shaped  drinking  cups  were  made  of  it  (44). 

Malachite  and  Azurite.  In  1778  the  Abbe  Felice  Fontana  ( 1730- 
1805)  published  analyses  of  malachite  and  azurite  in  the  Journal  de 
Physique.  According  to  Edmund  Cullen,  "The  illustrious  Fontana  was 
the  first  who  determined  the  true  nature  of  the  malachites"  (142,  280). 

The  British  mineralogist  Edward  Daniel  Clarke,  in  his  "Travels  in 
Various  Countries  of  Europe,  Asia,  and  Africa/*  described  a  most  unusual 
specimen  of  malachite.  "But  of  all  the  surprising  articles  in  natural  history 
I  saw  in  Moscow,"  said  he,  "the  most  worthy  of  admiration  were  two 
specimens,  the  one  of  malachite,  and  the  other  of  Siberian  emerald,  in 
the  audience  chamber  of  prince  Alexander  Galitzin.  They  were  placed 
alone,  independent  of  any  cabinet,  on  two  pedestals,  opposite  a  canopy, 
beneath  which  the  prince  and  princess  sat  on  days  of  ceremony.  .  .  . 
The  first,  or  the  mass  of  green,  carbonated  copper,  commonly  called 
malachite,  was  not  only  the  largest  appearance  of  that  substance  ever 
discovered,  but  also  the  most  beautiful.  It  was  found  in  the  Siberian 
mines;  and  was  matchless  in  every  circumstance  of  form  and  colour  which 
might  interest  a  naturalist  or  fulfil  the  wishes  of  the  lapidary.  Its  delicate 
surface,  of  the  most  beautiful,  silky  lustre,  exhibited  that  mammillary 
undulation,  and  those  conical  nodes,  which  decide  the  stalactite  origin 
of  the  mineral.  Its  interiour,  though  exquisitely  zoned,  was  entire  and 
compact;  and  for  the  mere  purpose  of  cutting  into  plates,  in  the  hands 
of  jewellers,  would  have  been  inestimable.  The  weight  of  this  enormous 
mass  must  have  been  at  least  a  ton.  For  this  specimen,  while  I  remained 
in  the  city,  a  dealer  offered  his  highness  six  thousand  roubles,  which 
were  refused"  (143). 

Verdigris.  In  ancient  times  verdigris  was  used  mainly  as  a  medica 
ment  but  sometimes  also  as  a  pigment  (144).  Theophrastus,  in  his 
"History  of  Stones,"  described  a  process  of  manufacturing  it  by  placing 
copper  over  the  lees  of  wine  (145).  According  to  Pedanios  Dioscorides 
of  Anazarba,  it  was  made  by  inverting  a  brazen  vessel  over  a  hogshead 
of  vinegar  or  by  hanging  brass  plates  above  the  vinegar  (146). 

The  Stockholm  papyrus  (third  or  fourth  century  A.D.)  gives  the 
following  recipe  for  preparing  verdigris  for  making  artificial  emeralds: 
"Clean  a  well-made  sheet  of  Cyprian  copper  by  means  of  pumice  stone 
and  water,  dry,  and  smear  it  very  lightly  with  a  very  little  oil.  Spread  it 


24  DISCOVERY  OF  THE  ELEMENTS 

out  and  tie  a  cord  around  it.  Then  hang  it  in  a  cask  with  sharp  vinegar 
so  that  it  does  not  touch  the  vinegar,  and  carefully  close  the  cask  so  that 
no  evaporation  takes  place.  Now  if  you  put  it  in  in  the  morning,  then 
scrape  off  the  verdigris  carefully  in  the  evening  .  .  .  and  suspend  it  again 
until  the  sheet  becomes  used  up.  However,  as  often  as  you  scrape  it  off 
again,  smear  the  sheet  with  oil  as  explained  previously.  The  vinegar  is 
[thus  rendered]  unfit  for  use"  (147). 

At  Montpellier  the  manufacture  of  verdigris  was  entirely  domestic. 
In  most  wine  farmhouses  there  was  a  verdigris  cellar  operated  by  the 
women  of  the  family  (148).  After  the  juice  had  been  pressed  out,  the 
skins  of  the  grapes  were  placed  in  alternate  layers  on  copper  plates.  As 
the  skins  became  acidic,  they  corroded  the  copper  (149). 

In  Geoffrey  the  Elder's  "Treatise  of  the  Fossil,  Vegetable,  and 
Animal  Substances  that  are  made  use  of  in  Physick,"  which  is  based  on 
lectures  which  he  began  to  deliver  in  1709  and  which  were  found  in 
good  order  among  his  papers  at  the  time  of  his  death,  he  stated  that 
"Various  Recrements  of  Copper  were  prepared  by  the  Ancients  and 
employed  in  Medicines  .  .  .  but  the  Aerugo,  or  Verdigrease,  is  the 
only  Recrement  now  in  use.  It  is  a  green  Rust  raised  in  Copper  Plates; 
the  Method  of  raising  it,  taken  from  the  Memoirs  of  the  Philosophical 
Society  of  Montpelier,  is  as  follows.  The  Husks,  Stones  &c.  of  Grapes, 
being  first  dried,  and  after  dipped  in  some  strong  Wine,  are  laid  for 
nine  or  ten  Days  in  wooden  or  earthen  Vessels,  till  they  begin  to  ferment. 
Then  being  squeezed  together  with  both  Hands,  they  are  formed  into 
Balls,  which  being  put  into  proper  earthen  Pots,  and  Wine  poured  upon 
them,  till  about  half  is  covered,  the  Vessels  have  a  straw  Lid  thrown  over 
them,  and  are  set  in  a  Wine  Cellar;  where  the  Balls  are  left  in  Maceration 
for  twelve  or  fifteen  Hours,  being  turned  every  four  Hours,  that  the  Wine 
may  penetrate  every  Part  of  them.  Afterwards  the  Balls  being  raised 
about  a  Finger's  breadth  above  the  surface  of  the  Wine,  and  set  upon 
wooden  Bars,  the  Vessels  are  shut  again,  and  left  in  that  State  for  ten  or 
twelve  Days  more.  After  which  time,  the  Balls  emit  a  strong  and 
penetrating  Scent,  and  are  then  fit  for  dissolving  Copper.  For  this  pur 
pose  they  are  broke  and  bruised  with  the  Hand,  that  the  outer  Part  of 
them,  which  is  driest,  may  be  exactly  mix'd  with  the  inner,  which  is  still 
moist  with  Wine;  then  they  are  stratified  with  Copper  Plates  in  the  same 
Vessels  upon  wooden  Bars,  the  Plates  making  always  the  lowest  Stratum, 
and  the  Balls  the  uppermost."  .  .  .  "Verdigrease,"  added  Geoffroy,  "is 
used  by  Painters  and  other  artists,  but  is  seldom  prescribed  inwardly  by 
Physicians.  It  is  often  used  outwardly."  .  .  .  (129). 

In  1798  J.-A.  Chaptal  described  the  improvements  which  had  been 
made  in  this  process  since  1750-53,  when  an  account  of  it  had  been 


ELEMENTS   KNOWN  TO  THE   ANCIENTS  2o 

published  in  the  Memoires  de  I' Academic  des  Sciences  of  Paris.  "The 
copper  used/'  said  he,  "formerly  came,  already  prepared,  from  Sweden. 
Today  it  is  obtained  from  various  smelting-houses  established  at  Saint-Bel, 
Lyons,  Avignon,  Bedarieux,  Montpellier,  etc."  (150). 

Copper  in  Spring  Waters.  Geoffroy  the  Elder  was  familiar  with 
certain  spring  waters  which  contain  copper  in  solution.  "There  are  some 
Springs  of  Copper-waters,  of  which  Vitriol  is  made  by  boiling,  and  Copper 
may  be  praecipitated  from  them  by  means  of  Iron,  which  has  made  some 
Persons  imagine  that  these  Waters  turned  Iron  into  Copper.  .  .  .  There 
is  a  famous  Spring  of  this  Kind  near  the  Carpathian  Mountains,  the 
Waters  of  which  corrode  Iron  thrown  into  it,  and  in  place  thereof  substi 
tute  Copper;  so  that  a  Horse-Shoe,  for  instance,  that  has  lain  several  Days 
in  this  Water  shall,  when  taken  out,  appear  not  to  be  Iron,  but  Copper" 
(129). 

In  1738  Matthew  Belius  (Bell),  a  Lutheran  pastor  at  Pressburg, 
Hungary,  observed  that  the  water  from  a  spring  at  Neusohl  had  the  same 
property  (151).  "This  water,"  said  he,  "which  seems  not  to  have  been 
known  in  the  time  of  Georg  Agricola,  was  discovered  in  the  year  1605 
during  the  insurrection  of  the  Botskay,  when  several  miners  hid  their 
property  and  especially  their  ironware  in  the  mines;  and  when  they  took 
it  out  again  after  the  retreat  of  the  Botskay  [Bocskay]  party,  they  found 
it  coated  with  a  crust  of  copper"  (151).  The  miners  used  the  spring 
water  medicinally,  and  prepared  copper  of  unusually  high  quality  from 
the  deposit  on  the  iron.  Belius  realized  that  this  was  not  an  alchemical 
transmutation  of  iron  into  copper  and  that  the  spring  derived  its  copper 
from  flowing  through  chalcopyrite  (151).  They  were  called  "cement- 
springs"  (152), 

A  similar  spring  in  Wicklow,  Ireland,  was  described  by  John  Bond 
in  the  Philosophical  Transactions  for  1753.  In  a  letter  to  Sir  Peter  Thomp 
son  he  wrote:  "You  may  remember  I  had  the  honour  of  spending  an 
evening  with  you  in  June  last,  and  happened  to  mention  a  spring  in  the 
county  of  Wicklow  in  Ireland,  which  was  supposed  to  have  the  surprising 
quality  of  changing  iron  into  copper.  But  your  constant  love  of  truth  and 
strong  aversion  to  vulgar  errors  made  you  doubt  the  fact.  .  .  .  Having 
soon  afterwards  occasion  to  go  to  Dublin,  I  went  to  the  spring,  which  is 
from  thence  about  38  miles,  and  made  several  experiments  on  the  water, 
the  result  of  which  I  beg  leave  to  present  you  with,  hoping  it  may  afford 
you  some  satisfaction  in  explaining  that  process,  of  which  you  so  justly 
doubted  the  account  given  by  some  credulous  authors,  who  mistook  it 
for  a  real  transmutation:  a  ridiculous  doctrine,  which  destroys  the  essen 
tial  qualities  of  bodies  which  were  impressed  by  the  Great  Creator  on  all 
material  substances.  .  .  . 


26  DISCOVERY  OF  THE  ELEMENTS 

"As  the  history  of  this  discovery  has  already  been  accurately  related 
in  several  papers  read  before  the  Royal  Society/'  said  Bond,  ".  .  .1  shall 
confine  myself  to  the  chemical  analysis  of  the  water.  .  .  .  This  water 
flows  from  a  rich  copper  mine,  and  is  of  a  sharp  acid  taste  and  light  blue 
colour.  It  is  received  and  collected  in  pits,  wherein  iron  bars  are  put, 
which,  after  lying  in  the  water  for  about  three  months,  are  intirely  [sic] 
consumed,  and  at  the  bottom  of  the  pits  a  quantity  of  copper,  greater 
than  that  of  the  iron,  is  found  in  the  form  of  coarse  sand.  This  fact  is 
confirmed  by  profitable  experiments  often  repeated  since  the  discovery, 
the  honour  of  which  is  due  to  Mr.  Matthew  Johnston,  a  worthy  old  gentle 
man,  and  one  of  the  proprietors  of  the  mine,  who  first  proposed  this 
method  of  collecting  the  copper  ..."  (153).  Bond  made  the  practical 
suggestion  that  "perhaps  an  easier  method  may  be  discover'd  of  separa 
ting  copper  from  its  ore  by  precipitation"  (153). 

Some  Famous  Copper  Mines.  The  word  copper  is  indicative  of  its 
Cyprian  origin.  Whether  the  Island  of  Cyprus  was  named  for  the  metal 
or  the  metal  for  the  island  would  be  difficult  to  decide  (98).  Copper 
was  mined  at  Cyprus  in  antiquity,  especially  in  the  foothills  of  the 
Trobdos  range  along  the  coast  from  Marium  to  Soli,  and  was  its  most 
important  product  (98)  Long  before  the  Roman  period,  copper  was 
exported  from  Cyprus  as  ore  and  as  ingots.  The  copper  mines  of  this 
island  are  still  productive  (98). 

The  earliest  metal  implements  from  Cypriote  tombs  are  not  true 
bronze  but  are  composed  of  copper  containing  only  a  slight  admixture 
of  tin,  which  may  have  been  introduced  from  the  use  of  a  slightly  stannif 
erous  copper  ore.  Part  of  the  ore  was  purposely  left  unreduced  in  the 
form  of  copper  oxide  in  order  to  give  greater  hardness  to  the  metal  ( 154) . 

The  great  copper  mine  at  Falun,  Sweden,  has  been  worked  for  more 
than  seven  centuries;  its  charter  is  dated  1288.  For  centuries  it  was 
Sweden's  greatest  source  of  material  wealth  (155).  In  1734  Emanuel 
Swedenborg  published  a  Latin  treatise  "Regnum  subterraneum  sive  min- 
erale  de  cupro  et  orichalco,"  in  which  he  devoted  several  chapters  to  this 
mine.  He  said  that  when  its  "foundations,  doors,  grottoes,  walls,  porticoes, 
halls,  and  columns  were  thrown  open  to  their  fullest  extent,  the  ore 
glittering  on  all  sides  with  a  ruddy  glow,  and  almost  blinding  the  eyes 
with  rays  of  golden  colour,"  the  guests  "seemed  to  be,  as  it  were,  intro 
duced  into  the  presence  of  Venus  [copper]  herself  sitting  as  a  bride  or 
newly  wedded  wife  in  her  most  splendidly  decorated  bridal  chamber" 
(156). 

Carl  von  Linne  (Linnaeus)  described  the  Falun  mine  as  follows: 
"...  Out  of  the  mine  a  constant  smoke  ascended.  Never  has  a  poet 
described  a  Styx,  nor  a  theologian  a  hell  so  awful,  as  that  seen  here,  for 


ELEMENTS  KNOWN  TO  THE   ANCIENTS  27 

upward  rises  a  poisonous,  stinging,  sulphurous  smoke,  which  taints  the 
air  all  round,  and  so  corrodes  the  ground  that  no  plants  can  grow  in  the 
neighbourhood.  .  .  .  The  drifts  are  dark  with  soot,  the  floor  of  slippery 
stone,  the  passages  narrow  as  if  burrowed  by  moles,  on  all  sides  incrusted 
with  vitriol,  and  the  roof  drips  corrosive  vitriolic  water  .  .  ."  (157). 
Grateful  for  his  safe  return  from  the  mine,  awed  by  its  grandeur,  and 
terrified  by  its  hazards,  Linne  wrote  an  anthem  (157). 

According  to  Ludwig  Darmstaedter,  the  German  copper  deposits  in 
the  Harz  were  worked  as  early  as  the  year  968  A.D.  In  1450  Nessler,  a 
metallurgist  of  Joachimsthal,  showed  that  siliceous  ores  could  be  worked 
by  roasting  them,  leaching  out  the  copper  vitriol  with  water,  and  deposit 
ing  the  copper  from  this  solution  on  iron  (158). 

Henry  Latrobe  stated  that  the  copper  mine  near  the  confluence  of 
the  Passaic  and  Hackensack  Rivers  in  New  Jersey  was  discovered  in  about 
1719  by  Arent  Schuyler  (159).  "The  ore/'  said  Latrobe,  "was  found 
where  it  appeared  on  the  side  of  the  hill;  was  easily  raised;  and,  as  the 
policy  of  England,  at  that  time,  prohibited  the  establishment  of  smelting 
works  or  manufactories  in  her  colonies,  it  was  packed  in  casks,  each 
containing  about  four  hundred  pounds,  and  exported,  in  its  state  of  ore, 
to  England.  ...  At  the  time  when  pure  copper  was  sold  in  England  at 
£75  sterling  per  ton,  the  ore  of  Schuyler's  mine  was  shipped  for  England, 
at  New  York,  at  £70  sterling  per  ton.  This  proves  the  uncommon  rich 
ness  of  the  ore,  and  the  small  expense  of  converting  it  into  metal." 

Per  Kalm,  a  great  Swedish  naturalist  who  visited  North  America  in 
1748-51,  spoke  of  a  fine  copper  mine  which  the  Dutch  settlers  "discovered 
upon  the  second  river  between  Elizabeth-town  and  New  York"  (160). 
They  had  learned  of  it  through  the  Indians,  who  smoked  tobacco  pipes 
made  of  copper  from  this  mine. 

In  1653  Pere  Francesco  G.  Bressani,  a  Jesuit  missionary  to  New 
France,  stated  in  his  report  that  "There  is  a  Copper  ore,  which  is  very 
pure,  and  which  has  no  need  of  passing  through  the  fire;  but  it  is  in 
places  far  distant  and  hard  to  reach.  ...  I  have  seen  it  in  the  hands  of 
the  Barbarians,  but  no  one  has  visited  the  place  ..."  (161). 

In  1660  one  of  the  Jesuit  fathers  (probably  Druillettes)  met  a  Chris 
tian  Indian  who  had  explored  the  Lake  Superior  region.  The  account 
states  that  this  lake  is  "enriched  in  its  entire  circumference  with  mines  of 
lead  in  a  nearly  pure  state;  with  copper  of  such  excellence  that  pieces  as 
large  as  one's  fist  are  found,  all  refined;  and  with  great  rocks  having 
whole  veins  of  turquoise"  ( 162 ) .  The  "turquoise"  was  probably  amethyst. 

The  Jesuit  explorers  of  Lake  Superior  compared  it  to  a  bow  and 
arrow,  the  Canadian  shore  being  the  bow,  the  southern  or  United  States 
shore  the  bowstring,  and  the  Keweenaw  promontory  the  arrow.  In  this 


28  DISCOVERY  OF  THE  ELEMENTS 

promontory  were  many  great  deposits  of  native  copper.  In  1669-70 
they  learned  that  the  island  most  famous  for  copper  was  called  Minong 
[Isle  Royale].  "Pieces  of  Copper,  mingled  with  the  stones/'  so  runs  the 
Jesuit  report,  "are  found  at  the  water's  edge  almost  all  around  the  Island, 
especially  on  the  South  side;  but  principally  in  a  certain  inlet  that  is  near 
the  end  facing  the  Northeast,  toward  the  offing,  there  are  some  very 
steep  clay  hills  where  are  seen  several  strata  or  beds  of  red  Copper,  one 
over  another,  separated  or  divided  by  other  strata  of  earth  or  of  Rocks. 
In  the  water  even  is  seen  Copper  sand  as  it  were;  and  from  it  may  be 
dipped  up  with  ladles  grains  as  large  as  a  nut,  and  other  smaller  ones 
reduced  to  sand.  This  large  Island  is  almost  all  surrounded  with  Islets 
that  are  said  to  be  formed  of  Copper  ..."  (163). 

Even  before  1778,  skilled  miners  were  sent  from  Redruth,  Cornwall, 
to  inspect  the  Lake  Superior  copper  deposits  (164).  The  Medical 
Repository  for  1802  recorded  the  failure  of  an  expedition  to  this  region. 
"Travellers,"  it  said,  "have  related  that  there  are  vast  beds  of  native 
copper  and  copper  ores  of  great  value  on  the  south  side  of  Lake  Superior, 
within  the  territory  of  the  United  States."  A  resolution  which  passed  both 
Houses  of  Congress  in  1800  authorized  the  President  of  the  United  States 
to  employ  an  agent  to  ascertain  on  what  terms  the  mines  might  be 
purchased  for  the  government.  Because  of  procrastination  this  opportu 
nity  was  lost  (165). 

In  1821  Henry  R.  Schoolcraft  published  a  report  in  the  American 
Journal  of  Science  on  the  native  copper  on  the  southern  shore  of  Lake 
Superior.  "The  first  appearances  of  copper,"  said  he,  "are  seen  on  the 
head  of  the  portage  across  Keweena  [sic]  point,  two  hundred  and  seventy 
miles  beyond  the  Sault  de  St.  Marie,  where  the  pebbles  along  the  shore 
of  the  lake  contain  native  copper  disseminated  in  particles  varying  in 
size  from  a  grain  of  sand  to  a  lump  of  two  pounds  weight  Many  of  the 
detached  stones  at  this  point  are  also  coloured  green  by  the  carbonate 
of  copper,  and  the  rock  strata  in  the  vicinity  exhibit  traces  of  the  same 
ore.  These  indications  continue  to  the  river  Ontonagon,  which  has  long 
been  noted  for  the  large  masses  of  native  copper  found  upon  its  banks" 
(166).  James  Douglas,  who  described  the  geology  of  this  region  in 
1874,  said  that  the  Calumet  Mine  had  been  discovered  about  thirteen 
years  earlier  (167). 

Copper  in  Plants  and  Animals.  As  early  as  1818  C.  F.  Bucholz 
detected  copper  in  vegetable  ash  (170,  169).  In  1850  F.  J.  Malaguti 
and  his  collaborators  detected  it  in  several  species  of  Fucus  taken  near 
Saint-Malo  (170).  "The  normal  presence  of  copper  in  organized  nature 
being  today  a  fact  generally  admitted,"  said  they,  "one  may  conclude  that 
if  terrestrial  plants  imbibe  this  metal  from  the  soil,  the  Fucus  must  obtain 


ELEMENTS  KNOWN  TO  THE   ANCIENTS  29 

it  from  sea  water,  that  is  to  say,  from  the  medium  in  which  they  live" 
(170,  281}.  J.  G.  Forchhammer  in  1865  noticed  the  presence  of  copper 
in  the  lime  salts  of  marine  animals,  in  the  ash  of  certain  seaweeds  and 
corals,  and  in  Fucus  vesiculosus  (171}. 

Professor  Jerome  Nicldes  of  Nancy  pointed  out  in  1867  an  easily 
overlooked  source  of  error  in  some  of  the  early  researches  on  the  diffusion 
of  copper  in  nature.  "Impressed  with  this  wonderful  diffusion  of  a  metal 
which  is  found  everywhere  save  in  the  reagents  employed  for  finding  it, 
...  it  appeared  to  me  that  there  was  some  source  of  error,  and  if  it  was 
not  in  the  reagents,  it  must  be  found  in  the  apparatus,  especially  the 
apparatus  used  for  the  incineration.  ...  In  fact,  the  Bunsen  burners 
are  generally  of  copper.  .  .  .  Besides,  when  such  a  burner  is  lighted, 
the  flame  is  often  seen  colored  blue  by  the  copper  which  is  volatilized 
.  .  .-  (168). 

In  1847  E.  Harless  discovered  the  presence  of  copper  in  the  blood  of 
the  octopus  Eledone  and  the  snail  Helix  pomatia  (172,  173).  Investiga 
tion  of  the  phenomenon  by  which  the  blood  and  tissues  of  certain  marine 
animals  turn  blue  on  exposure  to  air  finally  led  to  the  discovery  that  the 
blood  plasma  of  such  animals  contains  copper  combined  with  a  protein. 
Because  of  its  analogy  to  hemoglobin  and  its  ability  to  carry  oxygen, 
L.  Fredericq  in  1878  named  the  copper-containing  protein  in  the  blood 
of  Octopus  uulgaris  hemocyanin  (173,  174). 

Small  amounts  of  copper  occur  in  all  tissues  of  the  human  body. 
E.  B.  Hart,  H.  Steenbock,  J.  Waddell,  and  C.  A.  Elvehjem  of  the  Univer 
sity  of  Wisconsin  found  in  1928  that  "iron  salts  of  high  purity  when  fed 
at  levels  of  0.5  milligram  of  iron  six  times  per  week  were  ineffective  in 
correcting  a  progressive  anemia  in  rats  confined  to  a  diet  of  cow's  whole 
milk;  but  that  an  equal  amount  of  iron  fed  as.  the  ash,  or  acid  extract  of 
the  ash,  of  dried  lettuce,  of  yellow  corn,  or  of  beef  liver  was  very  potent 
in  restoring  to  normal  the  hemoglobin  of  the  blood  stream"  (175}.  Notic 
ing  the  pale  blue  color  of  some  of  these  ashes,  they  were  reminded  of  the 
copper  content  of  hemocyanin  and  its  ability  to  form  oxyhemocyanin. 
When  they  added  copper  sulfate  to  the  previous  diet,  their  anemic  rats 
rapidly  recovered  (175}. 

IRON 

Iron  articles  were  probably  made  by  the  Egyptians  twenty-five  or 
thirty  centuries  before  Christ,  but  because  the  metal  is  so  readily  corroded, 
iron  objects  of  great  antiquity  are  much  rarer  than  similar  ones  made  of 
gold,  silver,  or  copper  (25}.  Smelting  furnaces  for  iron  were  used  in 
ancient  times,  but  the  exact  nature  of  the  process  is  not  known. 


30  DISCOVERY  OF  THE  ELEMENTS 

Of  all  the  ancient  allusions  to  this  metal,  the  Biblical  ones  are  the 
most  interesting.  Who  can  forget  Job's  eloquent  words:  "Oh,  that  my 
words  were  now  written!  Oh,  that  they  were  printed  in  a  book!  That 
they  were  graven  with  an  iron  pen  .  „  ."  (13).  The  first  mention  of  iron 
in  the  Bible  is  in  the  fourth  chapter  of  Genesis.  It  refers  to  "Tubal-cain, 
an  instructor  of  every  artificer  in  brass  and  iron"  ( Gen.  4,  22) .  Theophile 
J.  Meek  translates  this:  "Tubal-cain,  the  forger  of  bronze  and  iron 
utensils"  (37). 

In  a  short  but  remarkable  discourse  on  Hebrew  mining,  Job  states 
that  "Iron  is  taken  out  of  the  earth"  (Job  28,  2).  This  passage  describes 
the  deep  shaft,  the  dark  galleries  and  tunnels  through  the  rock,  the  under 
ground  streams,  the  beautiful,  precious  minerals,  and  the  rugged,  hazard 
ous  life  of  the  miners.  The  iron  stylus  mentioned  in  Job  19?  24  was  one 
of  the  most  ancient  of  writing  instruments.  Iron  fishhooks  and  spears 
must  also  have  been  in  use  when  this  book  was  written:  "Canst  thou 
draw  out  leviathan  with,  an  hook?  .  .  .  Canst  thou  fill  his  skin  with 
barbed  irons?  or  his  head  with  fish  spears?"  (Job  41, 1,  7). 

In  the  third  chapter  of  Deuteronomy  there  appears  to  be  a  description 
of  an  enormous  iron  bed:  "For  only  Og  king  of  Bashan  remained  of  the 
remnant  of  giants;  behold  his  bedstead  was  a  bedstead  of  iron;  is  it  not 
in  Rabbath  of  the  children  of  Ammon?  nine  cubits  was  the  length  thereof, 
and  four  cubits  the  breadth  of  it,  after  the  cubit  of  a  man"  (Deut.  3,  11). 
Since  the  Hebrew  cubit  was  equal  to  about  seventeen  and  a  half  inches, 
this  bed  must  have  been  about  six  feet  wide  by  thirteen  feet  long. 
Theophile  J.  Meek  interpreted  this  to  mean  not  a  bed,  but  a  sarcophagus, 
and  James  Patrick  believed  that  it  was  made  not  of  iron  but  of  black 
basalt  (14,  37,  38,  48).  In  the  following  chapter,  the  land  of  bondage 
is  compared  to  an  iron  furnace:  "But  the  Lord  hath  taken  you,  and 
brought  you  forth  out  of  the  iron  furnace,  even  out  of  Egypt  ..." 
(Deut  4,  20). 

Joshua  mentioned  the  iron  chariots  of  the  Canaanites  (Josh.  17,  16). 
In  the  days  of  Saul  and  Jonathan,  there  was  no  smith  in  all  Israel  (I  Sam. 
133  19 )  ( 92 ) .  When  David  was  preparing  material  for  the  Temple,  iron 
was  abundant.  "And  David  prepared  iron  in  abundance  for  the  nails  for 
die  doors  of  the  gates,  and  for  the  joinings.  .  .  .  Now,  behold,  in  my 
trouble  I  have  prepared  for  the  house  of  the  Lord  an  hundred  thousand 
talents  of  gold,  and  a  thousand  thousand  talents  of  silver;  and  of  brass 
and  iron  without  weight;  for  it  is  in  abundance  .  .  . "  ( I  Chron.  22,  3,  14 ) . 
Saws,  harrows,  and  axes  of  this  metal  were  also  used  in  the  time  of  David 
(II  Sam.  12,31). 

When  Solomon  compiled  the  proverbs,  iron  tools  for  sharpening  must 
have  been  well  known:  "Iron  sharpeneth  iron;  so  a  man  sharpeneth  the 


ELEMENTS  K1SOWN  TO  THE  ANCIENTS  31 

countenance  of  his  friend"  (Prov.  27,  17).  Amos  mentioned  iron  thresh 
ing  implements,  and  Isaiah  spoke  of  cutting  down  thickets  with  iron 
(Amos  1,  3;  Isa.  10,  34).  Hezekiah's  workmen  who  diverted  the  water 
from  the  upper  springs  of  Gihon  and  allowed  it  to  flow  down  to  supply 
the  city  of  David  used  iron  tools  (II  Chron.  32,  30;  Ecclus.  48,  17)  (37). 

The  ancient  Hebrews  also  made  iron  cooking  utensils  such  as  the 
pan  mentioned  by  Ezekiel  ( Ezek.  4,  3 ) .  Six  centuries  before  Christ,  this 
metal  was  an  important  commodity  in  the  market  at  Tyre:  "Dan  also  and 
Javan  going  to  and  fro  occupied  in  thy  fairs:  bright  iron,  cassia,  and 
calamus,  were  in  thy  market"  (Ezek.  27,  19).  The  American  translation 
by  Smith  and  Goodspeed  and  the  modern  Spanish  translation  render  this 
as  "wrought  iron,"  or  "hierro  forjado"  (37,  91). 

Jeremiah  declared  that  "The  sin  of  Judah  is  written  with  a  pen  of 
iron  .  .  ."  (Jer.  17,  1). 

When  King  Nebuchadnezzar  conquered  Jerusalem,  he  took  all  the 
craftsmen  and  smiths  back  captive  to  Babylon  (II  Kings  24,  14r-16;  Jer. 
24,  1 ) .  The  trade  of  blacksmith  is  mentioned  several  times  in  the  Bible. 
In  the  Book  of  Isaiah,  the  Lord  says:  "Behold  I  have  created  the  smith 
that  bloweth  the  coals  in  the  fire,  and  that  bringeth  forth  an  instrument 
for  his  work  ..."  (Isa.  54,  16).  Isaiah  also  described  the  construction 
of  a  graven  image:  "The  smith  with  the  tongs  both  worketh  in  the  coals, 
and  fashioneth  it  with  hammers,  and  worketh  it  with  the  strength  of  his 
arms  ..."  (Isa.  44,  12).  Eccleciasticus  wrote:  "The  smith  also  sitting 
by  the  anvil,  and  considering  the  iron  work,  the  vapour  of  the  fire  waste th 
his  flesh,  and  he  fighteth  with  the  heat  of  the  furnace:  the  noise  of  the 
hammer  and  the  anvil  is  ever  in  his  ears,  and  his  eyes  look  still  upon  the 
pattern  of  the  thing  that  he  maketh;  he  setteth  his  mind  to  finish  his  work, 
and  watcheth  to  polish  it  perfectly"  ( Ecclus.  38,  28) . 

Iron  is  mentioned  also  in  the  New  Testament.  When  Peter,  for 
example,  was  delivered  from  the  prison  of  Herod  Agrippa  I,  he  passed 
through  "the  iron  gate  that  leadeth  unto  the  city"  of  Antioch,  Syria 
(Acts  12, 10). 

Rabbi  Joseph  Schwarz  wrote  in  1845  that  iron  was  found  near  the 
town  of  Dir  Al  Kamr,  in  Lebanon,  and  that  the  Jews  worked  the  mines 
and  made  horseshoes  from  the  metal.  Iron  was  also  obtained  from 
the  Egyptian  frontier  (96).  In  their  exploration  of  Edom  in  1934,  Nelson 
Glueck  and  his  party  of  explorers  found  rich  deposits  of  iron  ore  at 
Sabrah,  south  of  Petra  (89). 

The  metal  must  have  been  in  common  use  in  Pliny's  day,  for  he 
wrote  (12): 

It  is  by  the  aid  of  iron  -that  we  construct  houses,  cleave  rocks,  and  perform 
so  many  other  useful  offices  of  life.  But  it  is  with  iron  also  that  wars,  murders, 


32  DISCOVERY  OF  THE  ELEMENTS 

and  robberies  are  effected,  and  this,  not  only  hand  to  hand,  but  from  a  distance 
even,  by  the  aid  of  weapons  and  winged  weapons,  now  launched  from  engines, 
now  hurled  by  the  human  arm,  and  now  furnished  with  feathery  wings.  This 
last  I  regard  as  the  most  criminal  artifice  that  has  been  devised  by  the  human 
mind;  for,  as  if  to  bring  death  upon  man  with  still  greater  rapidity,  we  have 
given  wings  to  iron  and  taught  it  to  fly.  Let  us,  therefore,  acquit  Nature  of  a 
charge  that  belongs  to  man  himself.  .  .  .  Nature,  in  conformity  with  her  usual 
benevolence,  has  limited  the  power  of  iron  by  inflicting  upon  it  the  punishment 
of  rust;  and  has  thus  displayed  her  usual  foresight  in  rendering  nothing  in 
existence  more  perishable  than  the  substance  which  brings  the  greatest  dangers 
upon  perishable  mortality. 

Meteoric  Iron.  G.  W.  Wainwright  regards  some  iron  beads  which 
he  found  at  Gerzah,  Egypt,  about  fifty  miles  south  of  Cairo,  as  the  most 
ancient  pieces  of  iron  known.  They  date  back  to  3500  B.C.  or  earlier. 
Since  they  contain  7.5  per  cent  of  nickel,  they  must  have  been  made  from 
meteoric  material  (77).  Primitive  tribes  often  used  meteoric  iron  for 
weapons  and  tools,  and,  because  of  its  celestial  origin,  regarded  it  with 
great  reverence.  Under  the  title  "Our  Stone-pelted  Planet,"  H.  H.  Nin- 
inger  published  a  scholarly  and  entertaining  history  of  the  most  famous 
meteorites  (78). 

"The  first  tolerably  accurate  narration  of  the  fall  of  a  meteoric 
stone,"  said  W.  T.  Brande,  "relates  to  that  of  Ensisheim,  near  Basle,  upon 
the  Rhine.  The  account  which  is  deposited  in  the  church  was  thus:  A.D. 
1492,  Wednesday,  7  November,  there  was  a  loud  clap  of  thunder,  and  a 
child  saw  a  stone  fall  from  heaven;  it  struck  into  a  field  of  wheat,  and 
did  no  harm,  but  made  a  hole  there.  The  noise  it  made  was  heard  at 
Lucerne,  Villing,  and  other  places;  on  the  Monday,  King  Maximilian 
ordered  the  stone  to  be  brought  to  the  castle,  and  after  having  conversed 
about  it  with  the  noblemen,  said  the  people  of  Ensisheim  should  hang  it 
up  in  their  church  ..."  (176). 

Brande  also  mentioned  "the  great  block  of  iron  at  Elbogen  in 
Bohemia;  the  large  mass  discovered  by  Pallas,  weighing  1600  Russian 
pounds,  near  Krasnoyarsk  in  Siberia  .  .  .  and  those  noticed  by  Bruce, 
Bougainville,  Humboldt  and  others  in  America,  of  enormous  magnitude, 
exceeding  thirty  tons  in  weight.  That  these  should  be  of  the  same  source 
as  the  other  meteoric  stones  seems  at  first  to  startle  belief;  but  when  they 
are  submitted  to  analysis  and  the  iron  they  contain  found  alloyed  by 
nickel,  it  no  longer  seems  credulous  to  regard  them  as  of  meteoric  origin. 
We  find  nothing  of  the  kind  in  the  earth"  (176).  The  Elbogen  meteorite 
fell  in  about  1400  A.D.  (78). 

The  great  mass  of  iron  which  a  Cossack  found  at  Krasnoyarsk  in 
1749  interested  Professor  P.  S.  Pallas  so  much  that  in  1775  he  had  it 
brought  to  St.  Petersburg  for  investigation.  When  Torbern  Bergman 


ELEMENTS  KNOWN  TO  THE   ANCIENTS  33 

examined  it  five  years  later,  he  concluded  that  it  must  be  of  natural 
origin.  It  is  frequently  mentioned  in  the  literature  as  the  Pallas  meteorite 
(177).  According  to  G.  A.  Wainwright,  iron  is  the  only  metal  known  to 
occur  in  metallic  form  in  meteorites  ( 77 ) . 

Smelted  Iron.  The  earliest  known  finds  of  smelted  iron  are  from  Tell 
Asmar,  Mesopotamia,  and  Tall  Chagar  Bazaar  in  North  Syria.  One 
such  specimen  cannot  have  been  made  later  than  2700  B.C.  and  may  have 
been  produced  as  early  as  3000  B.C.  Since  it  contains  no  nickel,  it 
cannot  be  of  meteoric  origin  (79).  Although  the  Hittites  developed 
skill  in  smelting  iron,  they  kept  the  process  secret.  After  the  fall  of  their 
Empire  shortly  before  1200  B.C.,  the  iron  workers  were  dispersed  and 
the  true  Iron  Age  dawned  in  the  Near  East.  About  two  centuries  later, 
according  to  H.  H.  Coghlan,  this  craft  reached  Europe  (79). 

Many  Negro  tribes  of  Africa  have  worked  iron  for  centuries.  In 
his  "Mining  and  Metallurgy  in  Negro  Africa,"  Walter  Cline  states  that 
the  iron  and  slag  found  in  the  earliest  deposits  at  Zimbabwe  give  evidence 
that  iron  must  have  been  smelted  in  southeast  Africa  at  least  as  early  as 
the  eighth  century  A.D.  and  that  by  that  time  the  "iron  age"  in  this 
locality  was  well  advanced  (80).  According  to  A.  F.  Cronstedt,  the 
process  of  making  osmund  iron  was  known  to  the  Eskimos,  Yakuts,  and 
Ostiaks  of  Siberia  (81). 

Hematite.  Theophrastus  of  Eresus  was  familiar  with  hematite, 
which  he  called  "the  Haematites  or  Blood-stone,  which  is  of  a  dense, 
solid  Texture,  dry,  or,  according  to  its  Name,  seeming  as  if  form'd  of 
concreted  Blood"  (178).  He  also  knew  how  to  make  red  ocher  from  the 
yellow  variety,  a  process  which  he  attributed  to  "Cydias,  who  took  the 
Hint  of  it,  as  is  said,  from  observing,  in  a  House  which  was  on  fire,  that 
some  Ochre  which  was  there,  when  half  burnt,  assumed  a  red  Colour. 
The  way  of  making  the  factitious  is  this:  They  put  the  Ochre  into  new 
earthen  Vessels,  which  they  cover  with  Clay  and  set  in  Furnaces;  and 
these,  as  they  grow  hot,  heat  also  the  Ochre,  and  the  greater  Degree  of 
Fire  they  give,  the  deeper  and  more  strongly  Purple  the  Matter  becomes" 
(178).  Dioscorides  prepared  hematite  by  heating  magnetite  (179). 

Magnetite  (The  Lodestone).  Thales  stated  in  about  585  B.C.  that 
certain  iron  ores  and  iron  turnings  found  near  Magnesia  in  Lydia  have  a 
strange  power  of  attraction.  He  called  them  magnets  after  their  place  of 
origin  (180).  Theophrastus  said  of  the  lodestone  that  "the  greatest  and 
most  evident  attractive  Quality  is  in  that  Stone  which  attracts  Iron.  But 
that  is  a  scarce  stone,  and  found  in  but  few  Places"  (178). 

Pyrite,  Green  Vitriol,  and  Ocher.  In  1579  Matthias  Falconer  of 
Brabant  founded  at  Queenborough  the  first  plant  in  England  for  con 
verting  iron  pyrites  into  copperas  (ferrous  sulfate,  or  green  vitriol)  and 


34  DISCOVERY  OF  THE  ELEMENTS 

brimstone.  The  pyrite  occurred  in  large  quantities  in  Sheppey  and  on  the 
Essex  shore  (181).  Peter  Mundy,  who  toured  Europe  in  1639-47, 
described  another  process  used  at  "Quinburrow"  [Queenborough]  for 
making  copperas:  After  scrap  iron  had  been  boiled  in  "a  certain  liquor," 
branches  were  laid  in  the  hot  solution,  and  as  the  latter  cooled  it  deposited 
ferrous  sulfate  crystals  on  the  branches  (181). 

Charles  Hatchett  analyzed  magnetic  pyrite  and  stated  that  the 
discovery  of  iron  in  pyrite  is  comparatively  recent.  "According  to 
Henckel,"  said  he,  "this  was  first  noticed  by  our  countryman  Martin 
Lister,  a  member  of  this  learned  Society  [the  Royal  Society]  ..."  (182). 

When  Edward  Daniel  Clarke  visited  the  great  copper  mine  at  Falun, 
Sweden,  he  observed  great  stalactites  of  green  vitriol  hanging  from  the 
brick  roofs  of  the  levels  and  the  wooden  ducts  for  carrying  off  the  water. 
"The  whole  of  this  vitriol,"  said  Clarke,  "and  all  the  vitriolic  water  of  the 
mine  are  the  property  of  Assessor  Gahn.  .  .  .  The  water  of  the  mine  at 
Fahlun  is  impregnated  with  sulphuric  acid,  holding  copper  in  solution: 
but  in  its  passage  through  the  works,  whenever  it  comes  into  contact  with 
iron,  for  which  the  sulphuric  acid  has  a  greater  affinity,  a  portion  of  the 
sulphate  of  iron  being  then  exposed  to  evaporation,  is  gradually  concen 
trated;  and  either  crystallizes,  or  appears  in  beautiful  transparent  stalac 
tites  in  different  parts  of  the  mine.  But  the  product  of  this  deposit  is 
trifling,  compared  with  the  quantity  of  the  same  salt  which  is  procured 
from  the  vitriol-works  on  the  outside  of  the  mine;  to  which  the  water  of 
the  mine  is  conveyed  by  pumps  ..."  (183). 

"Formerly,  when  the  mine  was  richer,"  said  Clarke,  "they  made  no 
use  of  the  iron  pyrites,  which  is  dug  in  considerable  quantity7;  but  now  a 
work  is  established  for  roasting  this  mineral,  and  manufacturing  red-ochre 
as  a  pigment.  .  .  .  The  process  for  the  peroxidation  of  the  iron  is 
extremely  simple:  it  is  obtained  from  heaps  of  decomposed  sulphurets, 
or,  as  they  are  commonly  called,  pyrites,  which  have  been  long  exposed  to 
the  action  of  the  atmosphere.  Of  these,  a  lixivium  is  made;  in  which 
a  yellow  mud  subsiding,  affords  the  ochre,  which  is  submitted  to  the 
action  of  heat  in  a  long  furnace;  so  contrived,  as  that  the  flame,  drawn 
out  to  considerable  length,  may  act  upon  the  iron  oxide,  and  thus  convert 
it  into  red  ochre"  (183). 

In  1821  John  Locke  described  a  pyrite  mine  and  copperas  plant  at 
Strafford,  Vermont.  To  facilitate  crystallization  of  the  green  vitriol, 
branches  of  trees  were  put  into  the  evaporating  cisterns  as  nuclei  for  the 
crystals.  "The  branches,"  said  Locke,  "have  a  fine  crop  of  foliage  and 
fruit  composed  of  beautiful  green  crystals.  .  .  .  Everything  about  this 
mineral  manufactory  is  curiously  reddened  with  iron  rust.  When  a  dry 


ELEMENTS  KNOWN  TO  THE   ANCIENTS  35 

day  succeeds  a  rain  or  a  shower,,  the  whole  mine  becomes  covered  with 
a  white  crystalline  efflorescence  like  a  hoar  frost,  and  the  rain  water  which 
runs  down  into  the  cavities  of  the  mine  becomes  so  strong  a  solution  as 
to  crystallize.  Wherever  the  solution  dribbles  from  the  rocks  or  leaks 
from  the  cisterns,  large  stalactites  are  formed  so  precisely  like  icicles 
that  they  would  not  be  distinguished  from  them  were  it  not  for  their 
green  colour  .  .  ."  (184). 

Some  Famous  Iron  Mines.  The  Cerro  de  Mercado  in  Durango, 
north  central  Mexico,  one  of  the  largest  iron  ore  deposits  in  the  world, 
was  discovered  by  Gines  Vdsquez  de  Mercado  in  1552  (108). 

Herman  Boerhaave  (1668-1738)  said  in  his  "New  Method  of 
Chemistry"  that  "Iron  mines  are  common  in  most  countries  of  Europe: 
Norway,  Poland,  Germany,  France,  England,  &c.  abound  with  them; 
only  America,  which  is  so  plentiful  in  gold  and  silver  mines,  has  none  of 
iron;  and  accordingly,  the  natives  prefer  a  metal  of  so  much  use  infinitely 
beyond  their  own  treasures"  (185).  Although  the  Indians,  as  Boerhaave 
stated,  did  not  know  how  to  reduce  iron  ores,  the  New  England  colonists 
worked  the  bog  iron  ore  of  the  Saugus  River  near  Lynn,  Massachusetts, 
as  early  as  1643  (186). 

Per  Kalm  observed  in  1748—51  that  "Iron  is  dug  in  such  great  quan 
tities  in  Pennsylvania  and  in  other  American  provinces  of  the  English 
that  they  could  provide  with  that  commodity  not  only  England  but 
almost  all  Europe  and  perhaps  the  greatest  part  of  the  globe.  The  ore 
is  here  commonly  infinitely  easier  got  in  the  mines  than  our  Swedish  ore. 
For  in  many  places,  with  a  pick-axe,  a  crow-foot,  and  a  wooden  club,  it  is 
got  with  the  same  ease  with  which  a  hole  can  be  made  in  a  hard  soil:  in 
many  places  the  people  know  nothing  of  boring,  blasting,  and  firing;  and 
the  ore  is  likewise  very  fusible.  Of  this  iron  they  get  such  quantities  that 
not  only  the  numerous  inhabitants  of  the  colonies  themselves  have  enough 
of  it,  but  great  quantities  are  sent  to  the  West  Indies.  .  .  .  This  iron 
is  reckoned  better  for  ship-building  than  our  Swedish  iron  or  any  other, 
because  salt  water  does  not  corrode  it  so  much  ..."  (187). 

Kalm  visited  an  iron  works  at  Trois  Rivieres,  between  Quebec  and 
Montreal,  on  the  St.  Lawrence  River.  "The  ore  is  got,"  said  he,  "two 
French  miles  and  a  half  from  the  iron  works  and  is  carried  thither  on 
sledges.  .  .  .  This  iron  work  was  first  founded  in  1737  by  private  persons 
who  afterwards  ceded  it  to  the  king;  they  cast  cannon  and  mortars  here 
of  different  sizes,  iron  stoves  which  are  used  all  over  Canada,  kettles,  etc. 
.  .  .  They  have  likewise  tried  to  make  steel  here,  but  cannot  bring  it 
to  any  great  perfection  .  .  ."  (187). 

The  iron  ores  of  the  Lake  Superior  district  were  first  found  in  com 
mercial  quantities  near  Negaunee,  Michigan,  in  1844  by  Douglas  Hough- 


36  DISCOVERY  OF  THE  ELEMENTS 

ton,  state  geologist  (188).  Those  of  northern  Minnesota  were  first  re 
ported  by  J.  G.  Norwood  in  1850.  Shipping  of  iron  ores  from  the  Lake 
Superior  district  did  not  begin  until  four  years  later.  Each  of  the  great 
deposits  was  discovered  separately.  Charles  R.  Van  Hise  said  in  1903, 
"Discovered  only  about  ten  years  ago,  in  the  early  nineties,  the  Mesabi 
District  has  today  no  rival  in  its  production  or  reserve  of  iron  ore"  (188). 

Long  before  World  War  II  and  the  postwar  expansion  of  the  steel 
industry  had  seriously  depleted  the  vast  deposits  of  high-grade  ores  that 
can  be  mined  by  relatively  cheap  open-pit  methods,  Professor  Edward 
Wilson  Davis,  a  metallurgical  engineer  at  the  University  of  Minnesota, 
had  been  studying  the  possibility  of  utilizing  the  taconite,  a  hard,  iron- 
bearing  rock  that  can  be  mined  and  concentrated  only  with  considerable 
difficulty  and  expense.  Some  of  the  steel  companies  are  already  produc 
ing  great  quantities  of  taconite  concentrates  from  the  Mesabi  range. 
This  enormous  enterprise  was  recently  described  in  Readers  Digest  (189) . 

Iron  in  Vegetable  Ash.  Geoffroy  the  Elder  believed  that  the  iron 
detected  in  the  ash  of  plants  had  been  generated  or  produced  during  the 
ignition.  Etienne-Frangois  Geoffroy  was  born  in  Paris  on  February  13, 
1672,  a  son  of  Mathieu-Fran9ois  Geoffroy,  a  distinguished  apothecary. 
As  a  boy  he  listened  to  the  scientific  discussions  of  his  father's  friends  ( one 
of  whom  was  Willem  Homberg),  worked  at  the  lathe,  ground  lenses, 
made  models  of  machines,  and  studied  Italian.  When  he  was  twenty 
years  old,  his  father  sent  him  to  Montpellier  to  study  pharmacy.  During 
a  visit  to  England  he  gained  the  friendship  of  Sir  Hans  Sloane,  and  in 
Italy  and  the  Netherlands  he  met  some  of  the  greatest  scientists  of  his 
time. 

Mathieu-Frangois  Geoffroy  had  chosen  pharmacy  as  the  career  for 
his  elder  son  Etienne-Frangois  and  medicine  for  his  younger  son.  Etienne 
preferred  medicine,  however,  while  Claude- Joseph  followed  his  father's 
calling  and  became  a  famous  apothecary  and  chemist,  Geoffroy  the 
Younger. 

After  receiving  his  medical  degree,  Etienne-Frangois  studied  for  ten 
more  years  before  beginning  to  practice.  He  became  professor  of  materia 
medica  at  the  College  Royal  and  professor  of  chemistry  at  the  Jardin 
Royal.  In  1718  he  prepared  his  famous  table  of  chemical  affinities.  He 
died  on  January  6, 1731,  at  the  age  of  fifty-eight  years.  According  to  B.-B. 
de  Fontenelle,  he  was  gentle,  discreet,  even-tempered,  and  sympathetic 
(190,191,192). 

Using  a  magnet  to  test  for  iron,  E.-F.  Geoffroy  found  that  he  could 
detect  much  more  of  it  in  a  mixture  of  ignited  clay  and  linseed  oil  than 
he  could  in  the  original  clay,  and  concluded  that  iron  had  been  produced 
or  created/  Louis  L6mery  showed  in  1706-08,  however,  that  iron  can 


ELEMENTS  KNOWN  TO  THE  ANCIENTS 


37 


be  converted  (for  example,  by  treatment  with  an  acid)  into  a  non 
magnetic  condition.  When  he  heated  the  clay  alone  and  the  mixture 
of  clay  and  linseed  oil  to  a  moderate  temperature  under  identical  condi 
tions,  the  clay  yielded  a  red  substance  scarcely  attracted  by  the  magnet, 
whereas  the  mixture  of  clay  and  oil  yielded  a  black  substance  that  was 
much  more  magnetic.  He  concluded  therefore  that  the  iron  must  have 
been  present  originally  in  the  clay,  but  in  a  non-magnetic  form  which 


Georgius  Agricola,  1494- 
1555.  German  metallurgist. 
Author  of  "De  Re  Metallica," 
a  famous  Latin  treatise  on  min 
ing  and  metallurgy,  which 
has  been  translated  into  Eng 
lish  by  Ex-president  and  Mrs. 
Herbert  Hoover.  See  also 
ref.  (278). 


From  Bugge's  "Das  Buch  der  grossen  Chemiker" 


Geoffroy  had  failed  to  detect.  Lemery  also  pointed  out  that  there  is  no 
direct  relation  between  the  iron  content  of  an  ore  and  its  magnetic 
property  (193). 

He  then  went  on  to  show  that  "iron  often  fails  to  show  itself  even 
where  it  is  actually  present;  that  the  soil  contains  a  great  deal  of  it,  and 
that  its  ascent  in  plants  takes  place  very  easily.  One  can  scarcely  extract 
it  from  any  substance  in  which  one  could  not  correctly  surmise  that  it 
was  already  present;  and  conjecture  will  always  be  opposed  to  the 
artificial  production  of  a  metal  and  in  favor  of  its  pre-existence." 

Lemery  concluded  that  "one  does  not  produce  iron  merely  by 
making  it  sensitive  to  the  influence  of  the  magnet  .  .  .  and  [that]  the 
time  for  the  pleasant  hope  of  the  artificial  production  of  the  metals  has 
not  arrived"  (193). 

In  his  researches  on  iron  in  plants,  Lemery  also  discovered  that  by 
dissolving  iron  filings  in  spirit  of  niter  [nitric  acid],  he  could  make  an 
"iron  plant"  or  "tree  of  Mars."  When  Tsar  Peter  the  Great  visited  the 
Academy,  Lemery  showed  him  this  curious  chemical  vegetation.  The 


38  DISCOVERY  OF  THE  ELEMENTS 

"tree  of  Diana/'  or  "silver  tree,"  had  already  been  discovered  (194). 
Lemery  also  investigated  the  physiological  properties  of  iron  and  intro 
duced  into  medicine  the  use  of  Ethiops  martial,  which  came  to  be  known 
as  "black  powder  of  M.  Lemery"  (194). 

Louis  Lemery,  son  of  the  immortal  French  physician  and  chemist 
Nicolas  Lemery,  was  born  in  Paris  on  January  25,  1677,  and  studied  at 
Harcourt  College  (194).  Because  of  the  boys  gift  of  eloquence,  his 
uncle,  Louis  Lemery,  a  famous  attorney,  tried  to  induce  him  to  study 
law.  Young  Louis  preferred  his  father's  calling,  however,  and  at  the  age 
of  twenty-one  years  received  the  degree  of  doctor  of  medicine.  Two  years 
later  he  entered  the  Academy  to  study,  first  under  M.  de  Tournefort  and 
then  under  his  father  Nicolas  L&neiy. 

In  1702  Louis  Lemery  published  his  famous  "Treatise  on  Foods." 
For  thirty-three  years  he  served  as  physician  at  the  chief  hospital  (THotel 
Dieu),  where  he  always  attracted  a  large  number  of  medical  students 
(194).  Since  he  worked  with  extreme  facility  and  since  "his  knowledge, 
his  office,  and  his  laboratory  were  everywhere,"  he  was  able  to  write 
some  of  his  memoirs  at  the  chateau  of  his  royal  patient,  the  Princess  of 
Conti,  who  provided  him  a  quiet  retreat  for  his  scientific  research  (194). 

His  most  fruitful  chemical  work  was  done  in  three  fields:  the  nature 
of  iron  and  its  production,  niter  and  other  salts,  and  the  analysis  of 
plants  and  animals.  In  1731  he  succeeded  Geoffroy  the  Elder  as  professor 
of  chemistry  at  the  Jardin  Royal.  After  M.  Lemery  died  on  June  9,  1743, 
Dortous  de  Mairan  said  in  the  eulogy,  "He  was  kind  and  polished  in  his 
conversation,  capable  of  friendship,  generous  and  liberal.  Everything 
that  suffered  had  a  claim  upon  his  heart  and  his  property,  and  he  some 
times  gave  to  the  poor  sums  which  were  exorbitant  for  one  with  so  modest 
a  fortune"  (194). 

The  presence  of  iron  in  vegetable  ash  has  been  known  since  the 
beginning  of  the  eighteenth  century.  Although  iron  is  not  a  constituent 
of  the  chlorophyll  molecule,  a  plant  grown  in  a  culture  medium  entirely 
free  from  it  produces  no  chlorophyll.  According  to  Roscoe  W.  Thatcher, 
plants  take  iron  from  the  soil  in  the  smallest  proportion  of  any  of  the 
essential  elements.  Since  ferrous  compounds  are  toxic  to  plants,  only 
the  soluble  ferric  compounds  can  be  utilized  (195). 

Iron  in  Animals.  William  Lewis  stated  in  1746  in  his  annotated 
edition  of  George  Wilson's  "Compleat  Course  of  Chymistry,"  that  "red 
coral  calcined  in  an  open  fire  loses  its  colour  and  becomes  white;  from 
the  cak,  iron  may  be  extracted  by  applying  a  load  stone"  (196). 

Herman  Boerhaave  said  in  his  "Elements  of  Chemistry"  that  "Iron, 
which  seems  to  be  the  metal  whose  earth  most  closely  resembles  vegetable 
and  animal  earth,  also  has  a  great  deal  of  affinity  with  the  bodies  of 


ELEMENTS  KNOWN  TO  THE  ANCIENTS  39 

animals  and  plants,  and  may  perhaps  even  be  digested  by  them  in  some 
way.  That  is  why  it  is  an  excellent  remedy  for  various  diseases  of  the 
human  body  on  which  other  metals  act  too  violently"  (197). 

Iron  in  the  Blood.  According  to  P.-J.  Macquer's  "Dictionary  of 
Chemistry/'  the  first  scientist  to  investigate  thoroughly  the  cause  of  the 
red  color  of  the  blood  was  Vincenzo  Menghini,  who  found  that  the  red 
portion  of  it  contains  a  great  deal  of  iron  (198). 

Vincenzo  Menghini,  who  was  born  in  1705  in  Budrio,  Italy,  was 
highly  regarded  as  a  practicing  physician.  From  1737  to  the  close  of 
his  life  in  1759  he  taught  medicine  at  the  University  of  Bologna.  In 
1745  he  demonstrated  the  presence  of  iron  in  the  blood  corpuscles. 
Seeking  to  establish  the  presence  of  it  in  some  dogs  which  had  been  fed 
iron  preparations,  he  burned  some  blood  from  a  normal  dog,  expecting 
to  find  the  ash  free  from  iron.  To  his  surprise  he  saw  that  some  of  the 
particles  were  attracted  by  the  blade  of  a  magnetized  knife.  By  a 
series  of  precise  experiments  he  proved  that  this  iron  was  localized  in 
the  red  corpuscles  (199).  According  to  Mario  Betti,  who  published  a 
biographical  sketch  of  Menghini,  the  first  person  to  discover  the  presence 
of  iron  in  milk  was  Luigi  Galvani,  who,  however,  did  not  publish  his 
observation  (199). 

P.-J.  Macquer  said  that  "the  experiments  of  this  physician  [Menghini] 
are  very  beautiful  and  convincing,  but  M.  Rouelle  has  attained  a  new 
degree  of  accuracy  and  made  other  important  observations  on  the  salt- 
like  materials  contained  in  the  blood,  as  one  can  see  in  the  Journal  de 
Medecine  for  July,  1776.  According  to  the  observations  of  this  expert 
chemist,  the  blood  of  a  healthy  person  contains— after  drying,  burning, 
and  calcination  of  the  ash— natmm,  or  fixed  mineral  alkali,  common  salt, 
digestive  salt  [potassium  chloride]  in  small  quantity,  an  animal  or  cal 
careous  earth,  iron,  and,  finally,  carbon"  (198).  In  order  to  be  sure  that 
the  ash  contained  iron,  Rouelle  heated  it  with  reducing  agents  until  it 
was  readily  attracted  by  the  magnet.  In  his  experiments  he  used  the 
blood  of  cattle,  horses,  calves,  sheep,  hogs,  donkeys,  and  goats. 

After  stating  that  the  red  color  of  the  blood  might  be  due  to  the 
presence  of  iron,  Macquer  added:  "An  observation  from  practical  medi 
cine  agrees  well  with  this  view;  namely  that  mineral  water  containing 
iron,  iron  itself,  and  all  preparations  of  this  metal,  of  which  at  least  a 
considerable  part  passes  into  the  blood,  as  the  experiments  of  M.  Menghini 
have  shown,  are  the  best  remedy  one  can  use  for  chlorosis,  in  which 
disease  the  red  part  of  the  blood  is  almost  entirely  decolorized  or  dis 
colored"  (198).  Macquer  realized  that  the  iron  was  not  itself  the  coloring 
matter  of  the  blood  "but  perhaps  that  which  binds  this  pigment  and 
determines  its  action"  (198). 


40  DISCOVERY  OF  THE  ELEMENTS 

In  1667  the  Italian  physician  Carlo  Fracassati  published  a  paper  in 
the  Philosophical  Transactions  in  which  he  maintained  that  the  black 
color  of  the  blood  at  the  bottom  of  a  dish  filled  with  it  is  caused  not  by 
the  presence  of  a  "melancholy  humour"  but  by  its  lack  of  contact  with 
the  air.  When  he  exposed  the  dark  blood  to  air,  it  became  bright  red 
again  (200). 

Two  years  later  Richard  Lower  showed  that  arterial  blood  acquires 
its  brilliant  color  through  exposure  to  air  in  the  lungs  (200).  "I  have 
shown,"  said  fre,  "that  the  bright  red  colour  of  arterial  blood  is  not 
acquired  through  any  heating  in  the  heart  or  anywhere  else  at  any  time. 
We  must  next  see  to  what  the  blood  is  indebted  for  this  deep  red 
coloration.  This  must  be  attributed  entirely  to  the  lungs,  as  I  have  found 
that  the  blood,  which  enters  the  lungs  completely  venous  and  dark  in 
colour,  returns  from  them  quite  arterial  and  bright  .  .  ."  (201 ). 

The  fact  that  the  lower  part  of  a  quantity  of  blood  is  black  while 
the  surface  is  red  was  formerly  explained  by  assuming  that  the  black 
particles,  being  heavier,  sank  to  the  bottom.  In  1759  Giovanni  Francesco 
Cigna,  professor  of  anatomy  at  the  University  of  Turin,  showed  that 
when  the  dark  layers  of  the  blood  are  successively  exposed  to  the  air  by 
removal  of  the  red  surface  layer,  they  too  become  red.  At  his  request 
Father  Giovanni  Battista  Beccaria  tested  the  effect  of  a  vacuum  on  blood 
and  found  that  dark  blood  remained  dark  as  long  as  it  was  kept  in  a 
vacuum  but  became  red  when  subsequently  exposed  to  air  (202). 

William  Hewson,  in  his  "Experimental  Inquiry  into  the  Properties 
of  Blood,"  which  was  published  in  the  Philosophical  Transactions  in  1770, 
demonstrated  experimentally  that  "There  is  a  difference  between  the 
arterial  and  venous  blood  in  colour;  the  former  is  of  a  florid  red  like  the 
surface  of  the  Crassamentum  [clot],  the  latter  is  dark  or  blackish  like  the 
bottom  of  the  crassamentum.  This  change  in  its  colour  is  produced  as  it 
passes  through  the  lungs,  as  we  see  by  opening  of  living  animals;  and  as 
a  similar  change  is  produced  by  air  applied  to  blood  out  of  the  body,  it 
is  presumed  that  the  air  in  the  lungs  is  the  immediate  cause  of  this 
change;  but  how  it  effects  it,  is  not  yet  determined  .  .  ."  (203).  In  a 
footnote  Hewson  added  "That  this  change  is  really  produced  in  the  lungs, 
I  am  persuaded  from  experiments  in  which  I  have  distinctly  seen  the 
blood  of  a  more  florid  red  in  the  left  auricle  than  it  was  in  the  right  .  .  ." 
(202,203). 

With  the  early  microscopes  it  was  difficult  to  see  the  red  corpuscles 
of  the  blood  distinctly,  and  because  they  were  crowded  so  closely  to 
gether,  they  usually  appeared  merely  as  a  confused  mass.  Leeuwenhoek 
thought  they  were  spherical.  Father  de  la  Torre  of  Naples  however 
believed  them  to  be  annular.  After  diluting  the  blood  with  serum, 


ELEMENTS  KNOWN  TO  THE   ANCIENTS  41 

Hewson  was  able  to  observe  the  separate  red  corpuscles  more  distinctly 
and  to  note  that  they  were  "flat  as  a  guinea,"  with  "a  dark  spot  in  the 
middle"  which  "was  not  a  perforation"  ( 204 ) . 

Joseph  Priestley  found  that  the  constituent  of  the  atmosphere  which 
restores  the  bright  red  color  to  the  dark  blood  is  "dephlogisticated  air" 
(oxygen)  (202).  Although  Fourcroy  and  Vauquelin  believed  that  the 
iron  in  the  blood  was  combined  as  a  phosphate,  it  is  now  known  to  be 
present  in  a  far  more  complex  compound,  hemoglobin  (205).  M.  O. 
Schultze  found  that  analyses  of  hemoglobins  of  different  species  yielded 
concordant  values  of  0.335  per  cent  of  iron  ( 206 ) . 

In  the  summer  of  1840  Robert  Mayer,  while  performing  a  simple 
operation  of  bloodletting  on  board  a  Dutch  ship  in  Java,  was  so  startled 
by  the  bright  red  color  of  the  venous  blood  that  he  feared  for  a  moment 
that  he  might  have  opened  an  artery  by  mistake  (283).  Although  he 
was  unaware  of  Adair  Crawford's  experiments  on  the  influence  of  tem 
perature  on  the  color  of  venous  blood  in  living  animals,  which  were 
published  in  the  "Experiments  and  Observations  on  Animal  Heat  and  the 
Inflammation  of  Combustible  Bodies"  in  1788,  Mayer  reasoned  that  in  a 
hot  climate,  such  as  that  of  Java,  the  human  body  needed  less  internal 
combustion  in  order  to  maintain  its  temperature.  Two  years  later  he 
formulated  the  law  of  the  equivalence  between  heat  and  work  (283). 

LEAD 

The  unsurpassed  dramatist  who  wrote  the  Book  of  Job  mentioned 
lead  as  a  writing  material.  In  one  of  his  replies  to  Bildad,  Job  exclaims: 
"Oh  that  my  words  were  now  written!  oh  that  they  were  printed  in  a 
book!  That  they  were  graven  with  an  iron  pen  and  lead  in  the  rock  for 
ever.  For  I  know  that  my  redeemer  liveth  .  .  ."  (Job  19,  23-5)  (13). 
Commentators  disagree  as  to  the  exact  manner  in  which  this  writing  was 
done,  some  maintaining  that  the  characters  were  simply  engraved  on  a 
lead  plate  with  an  iron  stylus,  whereas  others  believe  that  the  stylus  was 
used  to  engrave  the  rock  and  that  molten  lead  was  afterward  poured 
into  the  etched  marks. 

After  the  pursuing  chariots  of  Pharaoh  had  been  engulfed  by  the 
Red  Sea,  Moses  and  the  children  of  Israel  sang  in  the  anthem  of  thanks 
giving,  "Thou  didst  blow  with  thy  wind,  the  sea  covered  them:  they  sank 
as  lead  in  the  mighty  waters"  ( Ex.  15, 10) .  In  the  time  of  Ezekiel  (nearly 
six  centuries  before  Christ),  lead  was  brought  to  the  great  Tynan  market 
from  Tarshish:  "Tarshish  was  thy  merchant  by  reason  of  the  multitude 
of  all  kind  of  riches;  with  silver,  iron,  tin,  and  lead,  they  traded  in  thy 
fairs"  (15). 


42  DISCOVERY  OF  THE  ELEMENTS 

In  the  time  of  Zechariah  (a  century  later),  lead  weights  were  in  use. 
"And  behold,  there  was  lifted  up  a  talent  of  lead  ..."  (Zech.  5,  7). 
Ecclesiasticus  said  of  King  Solomon,  "thou  didst  gather  gold  as  tin,  and 
didst  multiply  silver  as  lead"  (Ecclus.  47,  18). 

Lead  ores  are  widely  distributed  in  Nature,  and  are  easily  smelted. 
The  Babylonians  too  engraved  inscriptions  on  thin  plates  of  metallic  lead 
(10).  The  Romans  used  it  extensively  for  water  pipes,  writing  tablets, 
and  coins.  Unfortunately,  they  also  used  it  for  cooking  utensils,  and  lead 
poisoning  was  an  all-too-frequent  result.  A  few  very  small  lead  nuggets, 
some  of  which  are  believed  to  be  of  pre-Columbian  origin,  have  been 
found  in  Peru,  Yucatan,  and  Guatemala  (41 ). 

White  Lead.  Theophrastus  (372P-287  B.C.),  in  his  "History  of 
Stones,"  described  the  manufacture  of  "ceruse"  (basic  lead  carbonate,  or 
white  lead)  as  follows:  "Lead  is  placed  in  earthern  Vessels,  over  sharp 
Vinegar,  and  after  it  has  acquired  some  Thickness  of  a  kind  of  Rust, 
which  it  commonly  does  in  about  ten  Days,  they  open  the  Vessels,  and 
scrape  it  off,  as  it  were,  in  a  kind  of  Foulness;  they  then  place  the  Lead 
over  the  Vinegar  again,  repeating  over  and  over  the  same  Method  of 
scraping  it,  till  it  is  wholly  dissolved;  what  has  been  scraped  off  they 
then  beat  to  Powder,  and  boil  for  a  long  Time;  and  what  at  last  subsides 
to  the  Bottom  of  the  Vessel  is  the  Ceruse"  (207) .  By  the  time  of  Diosco- 
rides  (first  century  A.D.)  the  process  had  undergone  little  or  no  change 
(208). 

Dioscorides  also  described  minium,  distinguished  it  from  cinnabar, 
and  mentioned  its  use  for  the  painting  and  decorating  of  walls  (208). 

Marcus  Vitruvius,  architect  and  engineer  under  the  Emperor  Augus 
tus,  was  familiar  with  the  toxicity  of  lead  and  observed  that  the  laborers 
in  the  smelters  have  pale  complexions  because  of  their  prolonged  exposure 
to  lead  dust  and  vapor  (209). 

Some  Famous  Lead  Mines.  J.-P.  de  Tournefort,  who  visited  the 
Levant  in  1700,  wrote:  "Siphanto,  in  days  of  yore,  was  famed  for  its  rich 
Gold  and  Silver  Mines;  .  .  .  Besides  the  Mines  aforesaid,  they  have 
plenty  of  Lead;  the  Rains  make  a  plain  discovery  of  this,  go  almost  where 
you  will  throughout  the  whole  Island.  The  Oar  is  greyish,  sleek,  and 
yields  a  Lead  like  Pewter"  (210). 

The  lead  mines  of  Missouri  (formerly  known  as  the  lead  mines  of 
Louisiana)  were  discovered  in  1720  by  Philip  Francis  Renault  and  M. 
La  Motte,  who  afterward  worked  them  by  the  open-cut  method.  The 
famous  Burton  mine  was  discovered  more  than  half  a  century  later  and 
was  worked  wastefully  by  the  Spaniards.  In  1797  Moses  Austin  of 
Connecticut  sank  the  first  shaft,  installed  a  reverberatory  furnace,  and 
manufactured  shot  and  sheet  lead.  When  the  United  States  purchased 


ELEMENTS  KNOWN  TO  THE   ANCIENTS  43 

from  France  in  1803  the  vast  region  formerly  known  as  Louisiana,  the 
lead  industry  was  already  well  developed. 

In  about  1819  Henry  R.  Schoolcraft  visited  all  the  lead  mines  in  the 
Missouri  region,  traveling  on  foot  and  exploring  the  minerals  and  geologi 
cal  structures.  He  found  the  lead  mainly  in  the  form  of  the  sulfide, 
galena.  Zinc  sulfide,  or  sphalerite,  was  also  known  to  be  abundant,  but 
was  not  appreciated  at  that  early  period  because  satisfactory  metallurgical 
processes  were  lacking  (211).  This  Tri-state  Area  (Missouri,  Kansas,  and 
Oklahoma)  has  since  become  one  of  the  world's  leading  sources  of  both 
lead  and  zinc. 

TIN 

Among  the  spoils  of  war  which  the  Israelites  took  from  the  Midianites 
were  tin  and  the  other  five  metals  known  at  that  time:  "And  Eleazar  the 
priest  said  unto  the  men  of  war  which  went  to  the  battle,  This  is  the  ordi 
nance  of  the  law  which  the  Lord  commanded  Moses;  Only  the  gold,  and 
the  silver,  the  brass,  the  iron,  the  tin,  and  the  lead,  Every  thing  that  may 
abide  the  fire,  ye  shall  make  it  go  through  the  fire,  and  it  shall  be  clean 
.  .  . "  ( Num.  31, 21-3 ) .  Making  the  metals  "go  through  the  fire"  probably 
meant  a  gentle,  brief  ignition  to  remove  organic  matter  without  melting 
the  lead  and  tin  (92). 

Hebrew  metal  workers  recognized  tin  as  a  frequent  adulterant  of  the 
noble  metals:  "And  I  will  turn  my  hand  upon  thee,  and  purely  purge 
away  thy  dross,  and  take  away  all  thy  tin"  (Isa.  1,  25).  Alex.  R.  Gordon 
interprets  this  to  mean  "alloy"  instead  of  tin  (19).  EzekieFs  parable  of 
the  dross  in  the  furnace  also  recognizes  tin  as  a  base  metal  (Ezek.  22, 
18-22). 

After  the  Phoenicians  began  to  navigate  the  western  Mediterranean, 
they  brought  tin  from  Etruria,  Spain,  the  mouths  of  the  Loire,  the  Char- 
ente,  and  the  rivers  of  Brittany,  and  from  Cornwall  and  the  Scilly  Islands 
to  supply  the  demand  for  bronze  in  the  ancient  world  (268). 

Since  cassiterite  is  the  only  important  ore  of  tin,  it  must  have  been 
the  earliest  source  of  the  metal.  Although  the  Cassiterides,  or  tin  islands, 
vaguely  mentioned  by  classical  writers  were  usually  supposed  to  have 
been  named  for  the  ore,  cassiterite  may  possibly  have  been  named  for 
the  islands,  just  as  copper  may  have  been  named  for  Cyprus  and  bronze 
for  Brundisium  (Brindisi,  Italy)  (62).  Some  scholars  identify  the  Cassit 
erides  with  the  Scilly  Isles.  In  speaking  of  mirrors,  Pliny  the  Elder  stated 
that  "the  best  known  to  our  forefathers  were  made  at  Brundisium  from  a 
mixture  of  copper  and  stagnum"  (63). 

Bronze.  Long  before  metallic  tin  was  known,  bronze  was  in  common 
use.  In  Mesopotamia,  in  the  Indus  valley,  and  in  Egypt,  alloys  of  copper 


44  DISCOVERY  OF  THE  ELEMENTS 

and  tin  were  made  thirty  centuries  before  Christ.  Between  2100  and 
1700  B.C.,  the  Cretans  added  tin  to  copper  to  lower  the  melting  point. 
According  to  Wilhelm  Witter,  at  least  some  of  this  early  bronze  must 
have  come  from  the  ancient  tin  mines  in  Vogtland,  central  Germany, 
which  also  yielded  native  copper,  azurite,  and  malachite.  The  tin  con 
centrates  may  have  been  added  to  the  copper  ores  before  smelting,  first 
accidentally  and  later  intentionally,  to  harden  the  copper  and  make  it 
more  suitable  for  casting  (212,  213,  214). 

The  composition  of  Peruvian  bronze,  according  to  Hiram  Bingham, 
was  not  accidental.  Pure  tin  which  had  evidently  been  prepared  for  use 
in  casting  was  found  at  Machu  Picchu,  the  mountain  citadel  of  the  Incas. 
The  ancient  inhabitants  of  this  fortress  were  highly  skilled  metallurgists 
who  made  bronze  implements  of  varying  composition  according  to  the 
purposes  for  which  they  were  to  be  used.  No  artifacts  of  pure  tin  were 
found  there  (64).  Alexander  von  Humboldt  brought  home  from  his 
American  travels  a  well-forged  Peruvian  chisel  in  which  the  French 
chemist  N.-L.  Vauquelin  afterward  found  94  per  cent  of  copper  and  6  per 
cent  of  tin  (104). 

In  his  "Ancient  Egyptian  Materials  and  Industries,"  A.  Lucas  states 
that,  although  tin  ore  has  not  been  found  in  Egypt,  the  earliest  known 
artifacts  of  this  metal,  apart  from  bronze,  are  a  ring  and  a  pilgrim  bottle 
from  Egyptian  tombs  of  the  eighteenth  dynasty  ( 1580  B.C.  to  1350  B.C. ) 
(65). 

Homer's  "Iliad"  relates  how  Hephaistos,  the  lame  god  of  fire,  made 
a  shield  for  Achilles:  "And  he  threw  bronze  that  weareth  not  into  the 
fire,  and  tin  and  precious  gold  and  silver.  ..."  Among  the  many  decora 
tions  on  the  shield  was  a  vineyard  scene  in  gold  and  silver  with  a  fence 
of  tin  and  a  herd  of  cattle,  "and  the  kine  were  fashioned  of  gold  and 
tin.  ..."  The  greaves  were  of  "pliant  tin"  (66).  This  may  have  been 
a  tin  alloy,  however,  rather  than  the  pure  metal  (62). 

Herodotus  (484r-425  B.C. )  said  in  his  "History"  that  he  did  not  know 
of  any  "islands  called  the  Cassiterides  whence  the  tin  comes  which  we 
use.  .  .  .  Though  I  have  taken  great  pains,  I  have  never  been  able  to  get 
an  assurance  from  an  eye-witness  that  there  is  any  sea  on  the  further  side 
of  Europe.  Nevertheless,  tin  and  amber  do  certainly  come  to  us  from 
the  ends  of  the  earth"  (67). 

In  his  valuable  book  entitled  "The  Cornish  Miner,"  A.  K.  H.  Jenkin 
mentions  some  excavations  made  in  1925  at  the  famous  castle  of  Chun, 
near  St.  Just,  which  dates  back  to  300  to  200  B.C.  The  slag  found  in  the 
small  smelting  pits  there  contained  tin.  Thus  the  Cornish  tin  industry 
must  be  more  than  two  thousand  years  old.  The  earliest  known  charter 
of  the  Cornish  stannaries  is  dated  1201  ( 68 ) .  In  Book  V  of  his  "Commen- 


ELEMENTS  KNOWN  TO   THE   ANCIENTS  45 

taries  on  the  Gallic  War,"  Julius  Caesar  mentioned  the  production  of  tin 
in  the  midland  regions  of  Britain  (69). 

In  the  first  century  of  the  present  era,  the  Latins  referred  to  tin  as 
"plumbum  album"  to  distinguish  it  from  lead,  which  they  called  "plumbum 
nigrum"  (16).  Pliny  and  Dioscorides  mentioned  the  use  of  tin  coatings 
to  prevent  corrosion  of  copper  vessels  (17). 

When  Hernando  Cortes  arrived  in  Mexico  in  1519,  tin  from  a  mine 
in  Taxco  was  already  in  circulation  as  money  (40,  70).  "Some  small 
pieces  of  it,"  said  Cort6s,  "were  found  among  the  natives  of  a  province 
called  Tachco  [Tasco,  or  Taxco],  in  the  form  of  very  thin  coins;  and 
continuing  my  search  I  discovered  that  in  that  province  and  many  others 
this  was  used  as  money;  I  further  learned  that  it  was  mined  in  the 
province  of  Tachco,  twenty-six  leagues  from  this  city  [Temixtitan]"  (71).* 

Captain  Robert  Heath,  a  British  mathematician,  said  in  his  "Natural 
and  Historical  Account  of  the  Islands  of  Stilly/'  "Several  of  these  islands 
afford  tin,  and  some  also  lead  and  copper.  The  tin  is  discoverable  by  the 
banks  next  the  sea,  where  the  marks  of  the  ore  in  some  places  are 
visible  upon  the  surface;  this  I  was  assured  by  some  very  considerable 
Cornish  tinners,  in  the  year  1744.  .  .  .  Dionysius  Alexandrinus  speaks 
thus  of  the  Hesperides,  our  present  Scilly.  .  .  . 

Against  the  sacred  Cape,  great  Europe's  head 
Th'Hesperides  along  the  ocean  spread; 
Whose  wealthy  hills  with  mines  of  tin  abound, 
And  stout  Iberians  till  the  fertile  ground. 

They  were  called  Oestrymnides  by  Festus  Avienus  in  his  poem  De  Oris 
Maritimis,  or  Book  of  the  Coasts,  wherein  he  writes: 

The  isles  Oestrymnides  are  clustering  seen, 
Where  the  rich  soil  is  stord  with  lead  and  tin. 
Stout  are  the  natives,  and  untarnd  in  war  .    .    . 
They  skim  remote,  the  briny  swelling  -flood, 
With  leathern  boats  contriv'd  of  skins  and  wood" 

(215,216). 

In  the  time  of  Nicolas  L6mery  (1645-1715),  tin  was  "found  in  sev 
eral  mines,  principally  in  England,  which  is  therefore  called  the  Isle  of 
Tin.  .  .  .  The  purest  tin,"  said  he,  "is  that  which  comes  in  pigs  from 
Cornwall  .  .  ."  (217). 

In  the  seventeenth  century  Padre  A.  A.  Barba  visited  tin  mines  in 
Bolivia  which  had  been  worked  by  the  Incas  and  later  by  the  Spaniards. 

*  Temixtitan  and  Tenochtitlan  are  old  Aztec  names  for  Mexico  City. 


46  DISCOVERY  OF  THE  ELEMENTS 

"Also,"  said  he,  "in  this  Parish  of  San  Bernardo,  of  which  I  am  at  present 
the  incumbent,  and  about  a  quarter  of  a  league  from  the  Church,  there 
are  very  rich  Tin  mines"  (218). 

Tin  Dishes.  A.  S.  Marggraf  stated  in  1746-47  that  even  the  purest 
tin  then  obtainable  contained  arsenic.  "That  man  must  have  believed  tin 
to  be  especially  harmless  for  use  in  human  Life,"  said  he,  "is  evident  from 
the  great  number  of  vessels  of  it,  such  as  dishes,  plates,  pans,  tankards, 
teapots  and  coffee-pots  intended  for  food  and  drink,  and  various  utensils 
used  in  the  preparation  of  food,  as  well  as  the  tin-plating  of  copper  and 
iron  receptacles  and  the  many  vessels  used  in  chemistry  and  pharmacy, 
the  tin  and  tin-plated  still-heads,  stills,  caldrons,  basins,  cucurbits,  tubes, 
etc.;  all  this,  however,  holds  only  for  the  pure  unadulterated  native  tin" 
(219). 

Many  tin  alloys  containing  lead,  copper,  antimony,  and  bismuth  were 
also  in  use  in  Marggraf  s  time.  He  mentioned  three  kinds  of  unalloyed 
tin:  "first  the  Malaga,  reputed  to  be  the  best,  second  the  English,  and 
third  the  Saxon  and  Bohemian"  (219). 

Although  tin  ewers,  plates,  saltcellars,  tankards,  and  goblets  were  in 
common  use  in  seventeenth-century  France,  they  became  less  common  as 
the  art  of  enameling  developed  there.  Much  tin  was  then  consumed  in 
the  manufacture  of  enamels  (220). 

At  the  time  of  the  French  Revolution,  however,  tin  dishes  were  still 
to  be  seen  in  wealthy  homes  and  in  convents,  and  many  utensils  of  this 
metal  were  used  in  the  preparation  of  food  and  Pharmaceuticals.  The 
police  department  therefore  commissioned  Pierre  Bayen,  Hilaire-Marin 
Rouelle,  and  Charlard  to  examine  the  tin  to  see  whether  or  not  it  con 
tained  anything  deleterious  to  health.  Scarcely  had  the  investigation 
begun,  when  death  deprived  Bayen  and  Charlard  of  their  distinguished 
collaborator,  Rouelle  (220).  When  they  examined  tin  from  Banka  in 
the  East  Indies,  Malaga  in  Spain,  and  Cornwall,  England,  by  Marggraf  s 
method,  Bayen  and  Charlard  found  them  to  be  free  from  arsenic  and 
well  suited  for  household  use  (220). 

Tin  Plating.  In  320  B.C.,  Theophrastus  of  Eresus  mentioned  the 
plating  of  iron  with  tin  (221).  In  1820  Samuel  Parkes  described  several 
processes  for  this  art  which,  he  said,  flourished  in  Bohemia  long  before 
it  was  practiced  elsewhere  in  Europe.  "About  the  beginning  of  the 
seventeenth  century,"  said  he,  "mines  of  tin  were  discovered  in  Saxony, 
and  the  Elector  had  the  address  to  transplant  the  tin-plate  manufactory 
to  his  own  kingdom.  In  the  year  1665,  when  Mr.  Andrew  Yarrington 
visited  these  manufactories,  they  were  of  such  extent  as  to  employ  about 
80,000  workmen;  and  the  tin-plates  were  sent  to  all  parts  of  the  civilized 
world.  .  .  .  The  art  of  making  tin-plate  does  not  seem  to  have  been 


ELEMENTS  KNOWN  TO  THE   ANCIENTS  47 

practised  in  England  till  about  1720.  A  manufactory  was  then  estab 
lished  at  Pontypool,  in  Monmouthshire,  where  the  art  is  still  practised 
to  a  considerable  extent .  .  ."  (222). 

Timothy  Dwight,  in  his  "Travels  in  New  England  and  New  York/' 
described  the  tinware  trade  carried  on  by  pedlars  in  New  England, 
Virginia,  North  and  South  Carolina,  and  Georgia.  "Immediately  after 
the  late  war  with  Great  Britain,  which  terminated  in  1815,"  said  he, 
"ten  thousand  boxes  of  tinned  plates  were  manufactured  into  culinary 
vessels  in  the  town  of  Berlin  (Connecticut)  in  one  year."  This  business 
afterward  declined  (223). 

The  importance  of  tin,  as  Dr.  F.  J.  North  of  the  National  Museum 
of  Wales  pointed  out,  cannot  be  correctly  judged  from  the  quantities 
used.  Since  the  days  of  ancient  Rome,  it  has  been  applied  as  an 
extremely  thin  protective  layer,  or  tin  plate,  to  other  metals  to  make 
them  more  resistant  to  corrosion  and  safer  as  receptacles  for  foods  (224). 
In  1941  the  National  Museum  of  Wales  held  a  special  exhibition  entitled 
"Tin  through  the  Ages  in  Arts,  Crafts,  and  Industry." 


MERCURY 

"It  is  a  fluid 

but  does  not  moisten, 

and  runs  about, 

though  it  has  no  feet"  (225,  226). 

"On  vermil  beds  in  Idria's  mighty  caves 

The  living  Silver  rolls  its  ponderous  waves'  (227). 

Mercury  was  known  to  the  ancient  Chinese  and  Hindus,  and  has 
been  found  in  Egyptian  tombs  dating  back  to  1500  or  1600  B.C.  (10). 
Dioscoiides  mentioned  its  preparation  from  cinnabar  (18),  while  Pliny 
gave  a  method  of  purifying  it  by  squeezing  it  through  leather,  and  stated 
that  it  is  poisonous  (6).  Earle  R.  Caley  has  shown  by  quotations  from 
Aristotle,  Theophrastus,  Dioscorides,  Pliny  the  Elder,  Vitruvius,  and  the 
Leyden  Papyrus  of  the  third  century  A.D.  that  mercury  has  been  known 
much  longer  than  most  persons  realize.  He  states  that  cinnabar  was 
probably  the  only  mercury  compound  known  to  the  ancients  and  that 
they  used  it  both  as  a  pigment  and  as  a  source  of  the  metal  (49).  In  his 
"Metallurgic  Chemistry,"  C.  E.  Gellert  (1713-1795)  stated  that  "The 
only  ore  of  mercury  hitherto  known  is  native  cinnabar"  (50).  The  most 
ancient  specimen  of  quicksilver  known  is  probably  that  which  H.  Schlie- 
mann  found  in  a  little  cocoanut-shaped  amulet  in  an  Egyptian  tomb  at 
Kurna  dating  from  the  fifteenth  or  sixteenth  century  B.C.  (51,  52). 


48 


DISCOVERY  OF   THE  ELEMENTS 


Theophrastus,  a  disciple  of  Plato  and  successor  to  Aristotle,  described 
quicksilver  as  a  useful  substance  "obtained  from  native  Cinnabar,  rubbed 
with  Vinegar  in  a  brass  Mortar  with  a  brass  Pestle"  (53,  54,  55). 

"The  factitious  cinnabar,"  said  Theophrastus,  "is  from  the  Country 
a  little  above  Ephesus;  it  is  but  in  small  Quantities,  and  is  had  only  from 
one  Place.  It  is  only  a  Sand,  shining  like  Scarlet,  which  they  collect,  and 
rub  to  a  very  fine  Powder,  in  vessels  of  Stone  only,  and  afterwards  wash 
in  other  Vessels  of  Brass,  or  sometimes  of  Wood:  What  subsides  they 
go  to  work  on  again,  rubbing  it  and  washing  it  as  before"  (221,  228). 

Theophrastus  also  said  that  "one  Callius,  an  Athenian,  who  belonged 
to  the  Silver  Mines,  invented  and  taught  the  making  of  this  artificial 
Cinnabar.  He  had  carefully  got  together  a  great  Quantity  of  this  Sand, 
imagining  from  its  shining  Appearance  that  it  contained  Gold :  But  when 
he  had  found  that  it  did  not.,  and  had  had  an  Opportunity,  in  his  Trials, 


From  Biringuccio's  "Pirotechnia" 


Mercury  Stills,  1540 


of  admiring  the  Beauty  of  its  Colour,  he  invented  and  brought  into  use 
this  Preparation  of  it.  And  this  is  no  old  Thing,  the  Invention  being 
only  of  about  ninety  Years  Date;  Praxibulus  being  at  this  Time  in  the 
Government  of  Athens"  (226,  228). 

In  the  first  century  A.D.,  Dioscorides  Pedanios  of  Anazarbus,  Cilicia, 
gave  the  following  process  for  preparing  metallic  mercury:  "Putting  an 
iron  spoon  having  Cinnabaris  in  an  earthen  pot,  they  cover  the  Cup, 
dawbing  it  about  with  clay,  then  they  make  a  fire  under  with  coals;  and 
ye  soot  that  sticks  to  ye  pot,  being  scraped  off  &  cooled,  becomes 


ELEMENTS  KNOWN  TO  THE  ANCIENTS  49 

Hydrargyrum  [mercury].  It  is  found  also  in  ye  place  where  Silver  is 
melted,  standing  together  by  drops  on  ye  roofs.  And  some  say  that 
Hydrargyrum  is  found  by  itself  in  ye  mines.  But  it  is  kept  in  glassen,  or 
leaden,  or  tinnen,  or  silver  vessels,  for  it  eats  through  all  other  matter, 
and  makes  it  run  out"  (18,  56). 

The  Chinese  alchemist  Ko  Hung  (281-361  A.D.)  wrote  in  the  Pao 
Pu  Tzu,  "Many  do  not  even  know  that  mercury  comes  out  of  cinnabar 
(tan  sha).  When  told,  they  still  refuse  to  believe  it,  saying  that  cinnabar 
is  red,  and  how  can  it  produce  a  white  substance?  They  also  say  that 
cinnabar  is  a  stone— that  stones  when  heated  turn  to  ashes:  and  how  then 
can  anything  else  be  expected  of  tan  sha?"  ( 57 ) . 

Christophle  ( Christophe )  Glaser,  under  whom  Nicolas  Lemery  once 
studied,  stated  in  his  "Trait6  de  la  Chymie"  ("Chymischer  Wegweiser") 
that  natural  cinnabar  "consists  of  much  mercury  and  some  sulfur  and 
earth;  these  three  together  make  a  hard  body,  a  very  beautiful  red  color 
varying  in  brightness  according  to  the  purity  of  the  ore  and  the  place 
where  it  is  found.  It  is  brought  to  us  from  different  localities,  as  from 
Transylvania  and  Hungary  and  from  many  places  in  Germany;  the 
handsomest,  however,  is  found  in  Carinthia"  (229,  230). 

J.  M.  Hoppensack  stated  in  1795  that  the  mercury  mines  of  Almaden 
had  been  worked  for  at  least  2287  years  and  that  cinnabar  from  them  was 
sent  to  ancient  Rome  in  the  form  of  powder  or  sand  (58).  A.  de  Galvez- 
Canero  believed  that  the  Spanish  mercury  mines  have  been  worked  since 
the  third  or  fourth  century  B.C.  (28).  In  the  Memoires  of  the  Acad&nie 
des  Sciences  of  Paris  for  1719,  Antoine  Jussieu  published  a  first-hand 
description  of  the  great  mine  and  smelters  at  Almaden,  Spain,  which  he 
had  visited  two  years  previously  (233).  He  was  surprised  to  find  that 
the  crops,  trees,  and  inhabitants  were  not  injured  by  the  fumes,  and  that 
springs  near  the  mine  yielded  good  potable  water.  The  slaves  who 
worked  and  ate  in  the  mine  however  suffered  severely  from  mercury 
poisoning  (231). 

In  his  "Natural  and  Moral  History  of  the  Indies,"  Father  Jose  de 
Acosta  said  that  the  Incas  labored  long  in  the  Peruvian  mercury  mines 
without  knowing  what  quicksilver  was,  seeking  only  cinnabar,  or  ver 
milion,  to  use  as  war  paint  ( 59 ) .  The  Spaniards  discovered  the  mercury 
mines  of  Huancavelica  in  1566-67. 

Father  de  Acosta  told  how  Henrique  Garces,  a  native  of  Portugal, 
discovered  that  the  red  substance  llimpi  with  which  the  Indians  used  to 
paint  their  faces  was  the  same  as  the  Castilian  vermilion.  After  the  mines 
of  Palcas  in  the  territory  of  Guamanga  had  been  discovered  in  this  way, 
much  of  the  mercury  obtained  from  them  was  shipped  to  Mexico  to  be 
used  in  the  refining  of  silver  (232).  Pedro  Fernandez  de  Velasco,  who 


50  DISCOVERY  OF  THE  ELEMENTS 

had  observed  this  process  in  Mexico,  demonstrated  it  successfully  at 
Potosi  in  the  year  1571  or  1572  (232). 

When  he  demonstrated  de  Medina's  cold  amalgamation  process  to  the 
Viceroy,  the  latter  offered  him  suitable  reward,  ordered  him  to  make  the 
secret  known  at  Potosi  (Bolivia),  and  added  that  the  most  important 
wedding  in  the  world  was  about  to  take  place:  the  marriage  of  Mount 
Potosi  (silver)  to  Mount  Huancavelica  (mercury)  (60). 

A.  A.  Barba  of  Bolivia  stated  in  1640  in  his  "Arte  de  los  Metales,"  the 
first  treatise  on  American  metallurgy,  that  "There  was  very  little  use  or 
consumption  of  Quicksilver  before  the  beginning  of  this  new  Silver  age 
in  the  world,  then  they  only  wasted  it  in  Mercuiy  sublimate,  Cinabrio,  or 
Vermillion,  and  the  powders  made  thereof  called  Precipitate,  which  are 
also  called  in  Spain  the  powders  of  Juanes  de  Vigo,  which  have  been 
used  to  such  mischievous  purposes  that  the  world  was  said  to  have  too 
much  of  them,  although  in  bulk  and  quantity  then  they  had  but  little; 
but  since  it  hath  been  used  to  collect  the  Silver  together  out  of  Oar,  which 
is  ground  small  (an  invention  which  the  Ancients  had  scarcely  arrived 
to,  and  practised  it  but  very  little),  it  is  incredible  how  great  a  quantity 
is  consumed  by  the  Founders  of  Mettals  of  this  Kingdom:  for  if  the 
abundance  of  Silver  that  hath  gone  out  of  this  Kingdom  hath  filled  the 
world  with  riches  and  admiration,  by  it  may  be  estimated  the  consump 
tion  and  loss  of  Quicksilver,  which  after  a  most  extravagant  expence 
thereof  at  first,  being  now  by  good  experience  regulated  within  terms  of 
moderation,  is  found  to  be  equal  in  weight  to  the  Silver  extracted;  and 
very  seldom  that  the  wast  [sic]  is  so  little  ..."  (233). 

Baron  Alexander  von  Humboldt,  in  his  "Political  Essay  on  New 
Spain,"  gave  the  following  account  of  the  discovery  of  this  mine:  "The 
famous  mine  of  Huancavelica,"  said  he,  ".  .  .is  located  on  Mount  Santa 
Barbara,  south  of  the  city  of  Huancavelica.  .  .  .  The  discovery  of  the 
great  mercury  mine  is  generally  attributed  to  the  Indian,  Gonzalo  Abin- 
copa,  or  Navincopa;  but  it  certainly  occurred  long  before  the  year  1567, 
for  even  the  Incas  used  cinnabar  [llimpi]  for  their  cosmetics,  getting  it 
from  the  mountains  of  Palcas.  The  working  of  the  mine  on  Mt.  Santa 
Barbara,  for  the  crown,  did  not  begin  until  about  the  month  of  September 
in  1570,  the  year  in  which  Fernandez  de  Velasco  introduced  Mexican 
amalgamation  into  Peru"  (234). 

The  Mexican  method  referred  to  by  Father  de  Acosta  and  Baron 
von  Humboldt  was  the  cold  amalgamation,  or  patio,  process  introduced 
at  Pachuca  by  Bartolome  de  Medina  about  the  middle  of  the  sixteenth 
century.  As  early  as  March  4,  1552,  the  governing  princess  (Princesa 
Gobernadora )  in  Valladolid  acknowledged  an  urgent  request  for  mercury 
to  be  used  in  the  exploitation  of  silver  (28) .  In  this  process,  salt,  mercury, 


ELEMENTS  KNOWN  TO  THE  ANCIENTS  51 

and  copper  sulfate  were  used.  The  pulverized  mineral,  salt  brine,  and  a 
magistral  consisting  of  roasted  copper  and  iron  pyrites  and  mercury  were 
all  mixed  together  on  a  paved  floor.  Heat  was  required  only  for  the  last 
stage  of  the  process— the  decomposition  of  the  silver  amalgam  (60,  235). 

The  hot  amalgamation  process  for  silver  was  invented  by  Father 
A.  A.  Barba  (1569-1662)  soon  after  his  arrival  in  Charcas,  Bolivia  (28, 
236 ) .  His  "El  Arte  de  los  Metales"  was  devoted  mainly  to  the  metallurgy 
of  silver  and  gold  by  amalgamation  (235).  He  lived  to  be  ninety-three 
years  old  (237).  Captain  William  Betagh,  in  his  "Observations  on  the 
Country  of  Peru,"  gave  a  detailed  description  of  the  hot  amalgamation 
process  for  silver  as  practised  there  in  the  early  part  of  the  eighteenth 
century  (238). 

Baron  von  Humboldt  mentioned  three  occurrences  of  cinnabar  in 
New  Granada:  the  province  of  Antioquia;  Mount  Quindiu  in  the  Cordil 
leras;  and  a  place  between  Azogue  and  Cuenca  in  the  province  of  Quito. 
"The  discovery  of  the  cinnabar  of  Quindiu/'  said  he,  "is  owing  to  the 
patriotic  zeal  of  the  celebrated  botanist  Mutis,"  who,  in  the  months  of 
August  and  September,  1786,  had  some  mine-operators  examine,  at  his 
expense,  the  portion  of  the  granitic  Cordillera  which  extends  southward 
from  Nevado  de  Tolima  to  the  Rio  Saldana  (234).  Jose  Celestino  Mutis 
was  a  scholarly  Spanish  ecclesiastic  and  physician  who  became  professor 
of  philosophy,  mathematics,  and  natural  history  at  the  University  of 
Santa  Fe  in  Bogota,  New  Granada  (Colombia).  His  active  interest  in 
the  flora  of  South  America  led  him  to  carry  on  an  extensive  correspond 
ence  with  Linne  (Linnaeus)  (239).  A  description  of  the  Spanish  and 
the  Peruvian  quicksilver  mines  was  published  in  the  American  Journal 
of  Science  for  1868  (61). 

Indians  living  near  the  old  Santa  Clara  Mission,  about  fifty  miles 
from  the  present  city  of  San  Francisco,  California,  used  to  apply  red  and 
yellow  pigments  from  the  "Cave  of  the  Red  Earth"  near  there  for  personal 
adornment.  In  1845  Captain  Andres  Castillero  of  the  Mexican  Army, 
who  had  studied  chemistry  and  metallurgy  at  the  College  of  Mines  in 
Mexico  City,  discovered  near  the  Santa  Clara  Mission  an  ore  in  which 
he  easily  detected  metallic  mercury.  When  Don  Manuel  Herrera  of  that 
College  of  Mines  analyzed  specimens  of  this  ore  he  found  an  average 
mercury  content  of  35.5  per  cent  and  reported  that  some  pieces  were 
practically  pure  cinnabar.  Dr.  Henry  M.  Leicester  published  an  interest 
ing  article  on  the  history  of  the  New  Almaden  Mine  in  California  in  the 
Journal  of  Chemical  Education  (100).  When  gold  was  discovered  near 
Sutter's  Fort,  California,  in  1848  the  operation  of  the  gold  mines  that 
were  opened  up  during  the  "gold  rush  of  '49"  was  greatly  facilitated  by 
the  nearby  supply  of  mercury  for  amalgamation. 


52  DISCOVERY  OF  THE  ELEMENTS 

Corrosive  Sublimate  and  Calomel  A  method  for  preparing  a  rather 
pure  mercurous  chloride  (calomel)  was  known  to  Parisian  physicians 
before  1608  (83).  Oswald  Croll  prepared  it  by  a  secret  process,  and 
Jean  Beguin  in  his  "Tyrocinium  Chymicum,"  which  was  published  in 
1608,  described  the  process.  This  "mild  sublimate"  was  made  by  rubbing 
corrosive  sublimate  with  as  much  mercury  as  could  be  "killed"  or  made 
to  combine  with  it  (240,  241,  242}.  Calomel,  corrosive  sublimate,  and 
vermilion  have  been  manufactured  for  centuries  at  Hankow,  China  ( 243 ) . 

Chemists  of  India  prepared  both  chlorides  of  mercury  as  early  as 
the  twelfth  century  (244).  A  detailed  description  of  the  process  was 
given  in  the  thirteenth  or  fourteenth  century  ( 245 ) .  A  mixture  of  common 
salt,  brick  dust,  alum,  Indian  aloe,  and  mercury  was  heated  for  three  days 
in  a  closed  earthen  pot.  The  Japanese  and  Chinese  also  prepared  calomel 
by  similar  methods  (244). 

The  Freezing  of  Mercury.  Until  the  middle  of  the  eighteenth 
century,  chemists  believed  that  fluidity  was  an  essential  property  of 
mercury.  During  a  blizzard  on  the  twenty-fifth  of  December,  1759,  A. 
Braune  (or  Braun)  and  M.  V.  Lomonosov  of  the  Academy  of  Sciences 
of  St.  Petersburg  thought  it  would  be  interesting  to  see  how  much 
farther  the  temperature  could  be  lowered  by  artificial  means.  In  the 
presence  of  several  fellow  members  of  the  Academy,  they  packed  a 
mercury  thermometer  in  a  mixture  of  nitric  acid  and  snow.  The  mercury 
fell  rapidly  and  solidified  (246,  282).  Jakob  Fries  gave  a  vivid  account 
in  CrelFs  Annalen  of  his  experiences  with  freezing  mercury  in  January, 
1787,  during  a  cold  spell  (247).  P.  S.  Pallas  also  had  a  similar  experience 
with  the  natural  cold  of  Siberia  (248,  249). 


ANCIENT  NON-METALS 

SULFUR 

Since  sulfur  and  carbon  both  occur  uncombined  in  many  parts  of 
the  world  they  must  certainly  have  been  known  to  all  the  ancient  peoples. 

Although  the  word  brimstone  originally  meant  the  gum  of  the  gopher 
tree,  it  was  later  used  to  designate  other  flammable  substances,  especially 
sulfur  (86).  The  alchemists  used  the  word  sulfur  to  signify  combusti 
bility. 

The  exact  location  of  Sodom  and  Gomorrah  is  difficult  to  establish. 
The  Biblical  account  of  their  destruction  reads:  "Then  the  Lord  rained 
upon  Sodom  and  upon  Gomorrah  brimstone  and  fire  from  the  Lord  out 
of  heaven"  (Gen.  19,  24).  In  his  unsympathetic  interpretation  of  Job's 
suffering,  Bildad  set  forth  the  punishment  of  the  wicked,  and  added  that 


ELEMENTS  KNOWN  TO  THE  ANCIENTS 


53 


"brimstone  shall  be  scattered  upon  his  habitation"  (Job  18,  15).  Ezekiel 
prophesied  a  similar  upheaval  which,  he  said,  was  to  be  accompanied  by 
"a  great  shaking  in  the  land  of  Israel,  ...  an  overflowing  rain,  and  great 
hailstones,  fire,  and  brimstone"  (Ezek.  38,  19-22). 

Biblical  writers  used  the  flammability  of  sulfur  to  symbolize  tor 
ment  and  destruction.  In  speaking  of  the  condemned  Tophet,  Isaiah 
mentioned  liquid  sulfur:  "the  breath  of  the  Lord,  like  a  stream  of  brim 
stone,  doth  kindle  it"  (Isa.  30,  33). 

Although  there  seems  to  be  no  suggestion  in  the  Bible  that  the 
Hebrews  made  any  use  of  sulfur,  the  Greeks,  even  in  the  time  of  Homer, 


Woodcut  Showing 
Distillation  of  Sulphur 
in  1557 


employed  it  as  a  fumigant  (72).  After  the  killing  of  the  wooers  in  Book 
XXII  of  Homer's  "Odyssey,"  Odysseus  called  to  Eurycleia,  "Bring  sulphur, 
old  nurse,  that  cleanses  all  pollution  and  bring  me  fire,  that  I  may  purify 
the  house  with  sulphur"  (72). 

Pliny  described  the  Italian  and  Sicilian  deposits  in  great  detail, 
mentioning  the  use  of  block  sulfur  for  medicinal  purposes,  the  bleaching 
of  cloth  with  sulfur  vapor,  and  the  manufacture  of  sulfur  matches  and 
lamp  wicks  (19,  73).  Georgius  Agricola  (26)  stated  that  these  matches 
could  be  ignited  by  friction  on  stone  and  used  for  lighting  candles  and 
dry  wood.  He  also  left  no  doubt  as  to  his  opinion  of  gunpowder  when  he 
said:  "Sulfur  is  also  made  to  enter  into  that  powder— execrable  invention 
—which  hurls  iron,  brass,  or  stone  instruments  of  war  of  a  new  kind"  (20). 


54  DISCOVERY  OF  THE  ELEMENTS 

It  is  difficult  for  the  modern  chemist  to  understand  the  early  litera 
ture  of  sulfur,  for  the  name  was  incorrectly  used  to  designate  all  combus 
tible  substances.  In  the  tenth  century,  Jabir  believed  that  the  metals 
were  compounds  of  sulfur  and  mercury;  and  hence  these  two  elements 
came  to  have  great  significance  for  the  alchemists.  Abu  Mansur  men 
tioned  the  use  of  the  former  as  an  antidote  for  various  kinds  of  metallic 
poisoning,  and  Pseudo-Geber  told  how  to  prepare  milk  of  sulfur  by 
adding  vinegar  to  alkaline  sulfur  solutions  (34).  Some  scholars  regard 
the  Latin  work  "Invention  of  Verity,  or  Perfection,"  as  a  translation  of 
an  unknown  Arabic  treatise  by  Geber  (Abu  Musa  Jabir  ibn  Hayyan), 
who  lived  in  the  tenth  century  A.D.  Professor  Julius  Ruska  believed, 
however,  that  Geber  (Jabir)  and  Pseudo-Geber  (the  author  of  the 
"Invention  of  Verity")  must  have  been  separated  by  five  centuries  of 
time  (35). 

The  sulfur  from  which  Cort6s  and  his  daring  conquistadores  made 
their  first  gunpowder  was  obtained,  so  he  said,  from  the  rumbling, 
smoking  crater  of  Mount  Popocatepetl  (70).  In  a  letter  to  Charles  V, 
written  from  Temixtitan  on  October  15,  1524,  he  said,  "As  for  sulphur, 
I  have  spoken  to  Your  Majesty  of  that  mountain  in  the  province  of  Mexico 
which  smokes.  A  Spaniard  [Francisco  Montano]  descended  by  means 
of  a  rope,  seventy  or  eighty  fathoms,  and  obtained  a  sufficient  quantity 
to  last  us  in  our  need;  but  henceforward  there  will  be  no  necessity  of 
going  to  this  trouble  because  it  is  dangerous  and  I  shall  always  write  to 
obtain  these  things  from  Spain"  (76). 

Until  1849  there  seems  to  have  been  no  repetition  of  this  exploit. 
During  the  eighteen-fifties,  however,  intrepid  miners,  or  volcaneros,  used 
to  make  the  difficult  ascent  of  this  mountain.  After  being  lowered  by 
a  windlass  into  the  stifling  crater,  they  used  to  collect  about  ten  25-pound 
sacks  of  sulfur,  which  they  pushed  over  the  rim  of  the  crater  and  allowed 
to  slide  down  the  steep,  snow-covered  slope  of  the  mountain.  At  the 
Tlamacas  rancho  the  sulfur  was  purified  by  distillation  (70).  Norman 
J.  Harrar  described  these  hazardous  operations  in  the  Journal  of  Chemical 
Education. 

In  the  year  1700,  when  Joseph-Pitton  Tournefort  was  traveling  in 
the  Levant,  he  noticed  the  common  occurrence  of  sulfur  in  volcanic 
regions  near  the  sea.  "Such,"  said  he,  "are  the  famous  Vulcanoes  [sic] 
that  vomit  Flames  of  Fire;  Vesuvius,  Stromboli,  Mount  Aetna,  Mountains 
in  Ireland,  Fayal,  Pic-Teneriffe.  In  these  Islands  and  on  the  Coasts  of 
the  Terra-firma  of  America  [Panama],  there  are  Fires  which  have  been 
burning  from  the  beginning  of  the  World.  .  .  .  The  Sulphur  of  Milo 
[the  Island  of  Melos]  is  very  beautiful,  and  has  a  greenish  shining  Cast, 
which  made  the  Ancients  prefer  it  to  that  of  Italy  ..."  (250). 


ELEMENTS  KNOWN   TO  THE   ANCIENTS  55 

In  1759  Count  Vincenzo  Masini  (1689-1762)  of  Cesena,  Italy,  pub 
lished  a  patriotic  poem  on  sulfur,  in  which  he  described  its  extraction, 
purification,  and  uses.  Signor  Gino  Testi  has  published  extracts  from  this 
poem,  with  explanatory  notes  (74).  In  eloquent  Italian  verses  Count 
Masini  gave  poetic  expression  to  Giorgio  Baglivf  s  belief  that  vegetables 
and  animals  exert  an  influence  over  the  formation  of  the  metals  and  the 
so-called  semi-metals 

"...   Within  the  rocks,  among  the  thorns, 
Between  the  cliffs,  sulfur  takes  root; 
For  gold,  silver,  copper.,  iron,  and  sulfur 
Likewise  are  plants"  (74)* 

Count  Masini  also  expressed  dramatically  the  relation  between  sulfur  and 
volcanic  action. 

The  Abbe  Lazaro  Spallanzani  (1729-1799)  described  the  sulfurous 
fumes  of  Vulcano,  and  added  that  "Above  these  fumes  there  is  a  plain, 
of  no  great  extent,  which  one  is  at  first  afraid  to  venture  on,  from  the 
subterranean  noise  heard  there,  and  from  the  shaking  of  the  ground  when 
struck  with  the  foot.  ...  On  this  plain  it  was  that  formerly  stood  the 
furnaces  in  which  the  sulphur  of  Vulcano  was  purified.  But  this  useful 
labour  has  long  since  been  abandoned  .  .  .  nor  was  it  abandoned  because 
the  quantity  of  sulphur  obtained  was  too  little  .  .  . ,  as  the  vein  is  very 
rich  and  even  inexhaustible.  The  real  cause  why  the  inhabitants  of 
Lipari  no  longer  continued  this  work  was  that  the  ground  .  .  .  grows 
hotter  the  deeper  it  is  dug  into  .  .  . ,  to  which  is  to  be  added  the  offensive 
stench  of  the  sulphureous  fumes  .  .  ."  ( 75 ) . 

In  the  latter  part  of  the  eighteenth  century,  A.-L.  Lavoisier  and  his 
adherents  regarded  sulfur  as  an  element.  As  late  as  1809,  however, 
Sir  Humphry  Davy  believed  that  it  contained  oxygen  and  hydrogen  as 
essential  constituents  and  that  it  was  similar  in  composition  to  the  resins 
(30,  33).  Experiments  by  A.  Berthollet,  son  of  C.  L.  Berthollet,  had 
indicated  that  sulfur  contains  hydrogen.  From  his  own  experiments 
with  Sicilian  sulfur  in  1808,  Sir  Humphry  concluded  that  "'the  existence 
of  hydrogen  in  sulphur  is  fully  proved"  and  that  "sulphur,  in  its  common 
state,  is  a  compound  of  small  quantities  of  oxygen  and  hydrogen  with  a 
large  quantity  of  a  basis  that  produces  the  acids  of  sulphur  in  combustion 
..."  (30).  In  1809  Gay-Lussac  and  Thenard  thoroughly  established 
the  elementary  nature  of  sulfur  (31,  32). 

*  "     .    .   Entro  le  baize 

Fra  dumi,  e  fra  dirupi  il  zolfo  aligna; 

Che  piante  e  vegetabili  pur  sono 

L'oro,  I'argento,  il  rame,  il  ferro,  il  zolfo  ..."  (74) 


56  DISCOVERY  OF  THE  ELEMENTS 

By  1810  Davy  had  changed  his  views  and  suspected  "a  notable 
proportion  of  oxygen  in  Sicilian  sulphur,  which  is  probably  owing  to 
the  presence  of  oxide  of  sulphur.  .  .  .  Considering  the  manner  in  which 
sulphur  is  procured  in  Sicily,  it  might  be  expected  to  contain  oxygen; 
when  taken  from  the  mine,  the  limestone  rock  containing  it,  broken  into 
small  fragments,  is  subjected  to  heat  in  a  kind  of  kiln;  whilst  a  small 
portion  of  the  sulphur  is  burnt,  and  ascends  into  the  atmosphere  in  the 
form  of  sulphurous  acid  gas,  the  greater  part  of  it  melts,  sinks,  and  flows 
out  through  an  opening  designed  to  give  issue.  This  process  I  witnessed 
at  the  extensive  sulphur  mines  in  the  neighbourhood  of  Gujenti  [Girgenti, 
or  Agrigentum];  and  I  believe  it  is  generally  in  use  throughout  the  sulphur 
districts"  (30). 

When  Davy  allowed  "oxymuriatic  acid  gas"  (chlorine)  to  react  with 
moist  sulfur,  he  obtained  hydrogen  chloride  and  oxygen.  When  he 
repeated  the  experiment,  using  Sicilian  sulfur  dried  over  calcium  chloride, 
"no  oxygen  gas  was  evolved  and  not  a  cubical  inch  of  muriatic  [hydro 
chloric]  acid  .  .  .  and  it  was  found  that  between  16  and  17  cubical  inches 
of  oxymuriatic  acid  gas  [chlorine]  had  disappeared;  the  whole  of  the 
sulfur  was  sublimed  in  the  gas,  and  the  liquor  formed  was  of  a  tawny- 
orange  colour"  [probably  sulfur  monochloride]  (SO). 

Sulfur  in  Louisiana  and  Texas.  Prospectors  who  were  boring  for 
petroleum  in  Louisiana  in  1865  discovered  a  great  sulfur  deposit  beneath 
a  layer  of  quicksand  five  hundred  feet  thick  (251).  After  several 
companies  had  failed  in  all  attempts  to  exploit  this  sulfur,  Herman  Frasch 
in  about  1890  began  to  study  the  problem.  His  method  of  attack  is 
carefully  recorded  in  his  address  of  acceptance  of  the  Perkin  Medal  in 
1912. 

"To  meet  the  extraordinary  conditions  existing  in  this  deposit," 
said  he,  "I  decided  that  the  only  way  to  mine  this  sulphur  was  to  melt  it  in 
the  ground  and  pump  it  to  the  surface  iri  the  form  of  a  liquid.  ...  At 
that  time,  the  drilling  of  a  well  in  an  alluvial  deposit  containing  quick 
sand,  etc.,  was  a  very  tedious  task,  and  it  took  from  six  to  nine  months  to 
get  through  the  alluvial  material  to  the  rock-work  which  we  do  today 
in  three  days.  .  .  .  When  everything  was  ready  to  make  the  first  trial, 
...  we  raised  steam  in  the  boilers,  and  sent  the  superheated  water  into 
the  ground  without  a  hitch.  If  for  one  instant  the  high  temperature 
required  should  drop  below  the  melting  point  of  sulphur,  it  would  mean 
failure.  .  .  . 

"After  permitting  the  melting  fluid  to  go  into  the  ground  for  twenty- 
four  hours,"  continued  Mr.  Frasch,  "I  decided  that  sufficient  material 
must  have  been  melted  to  produce  some  sulphur.  The  pumping  engine 

started  on  the  sulphur  line,  and  the  increasing  strain  against  the 


ELEMENTS  KNOWN   TO  THE  ANCIENTS  57 

engine  showed  that  work  was  being  done.  More  and  more  slowly  went 
the  engine,  more  steam  was  supplied,  until  the  man  at  the  throttle  sang 
out  at  the  top  of  his  voice,  'She's  pumping/  A  liquid  appeared  in  the 
polished  rod,  and  when  I  wiped  it  off  with  my  finger  I  found  my  finger 
covered  with  sulphur.  Within  five  minutes  the  receptacles  under  pres 
sure  were  opened,  and  a  beautiful  stream  of  the  golden  fluid  shot  into  the 
barrels  we  had  ready  to  receive  the  product.  .  .  .  When  everything  had 
been  finished,  the  sulphur  all  piled  up  in  one  heap,  and  the  men  had 
departed,  ...  I  mounted  the  sulphur  pile  and  seated  myself  on  the 
very  top.  It  pleased  me  to  hear  the  slight  noise  caused  by  the  contraction 
of  the  warm  sulphur,  which  was  like  a  greeting  from  below  .  .  . "  ( 251 ) . 

In  presenting  the  Perkin  Medal  to  Mr.  Frasch,  Dr.  C.  F.  Chandler 
said,  "At  present  the  Louisiana  deposit  supplies  this  country  with  sulphur 
and  might  supply  large  quantities  to  European  countries.  Fortunately 
the  company  is  owned  by  a  few  broad-minded  and  large-hearted  men 
who  could  not  be  induced  to  bring  starvation  and  ruin  upon  the  two 
hundred  and  fifty  thousand  people  dependent  upon  the  mining  of  sulphur 
in  Sicily"  (251).  Mr.  Frasch  said  that  great  credit  was  also  due  the 
Italian  government  for  averting  unemployment  and  misery.  These  great 
American  sulfur  deposits  also  extend  into  Texas. 

Herman  Frasch  was  educated  in  Germany  as  an  apothecary's  appren 
tice,  and  came  to  the  United  States  at  the  age  of  sixteen  years  (274). 
After  spending  most  of  his  life  in  this  country  and  making  many  notable 
contributions  to  chemical  engineering,  he  lived  in  retirement  in  France, 
where  he  died  in  1914  at  the  age  of  sixty-two  years  (252). 

Sulfur  in  Plants.  The  presence  of  sulfur  in  plants  was  first  demon 
strated  in  1781  by  Nicolas  Deyeux,  who  detected  it  in  the  roots  of  the 
dock  (Rumex  patientia),  the  cochlearia,  and  the  horse  radish  (269,  270). 
Scheele,  however,  unable  to  confirm  the  discovery,  thought  that  the 
plants  which  Deyeux  had  analyzed  had  perhaps  grown  near  "hepatic 
air"  [hydrogen  sulfide]  or  pyrite  (271).  Sulfur  is  now  known  to  be 
essential  for  plant  growth.  In  many  early  plant  analyses  only  the  non 
volatile  sulfur,  which  appeared  as  sulfates  in  the  ash,  was  determined. 
Modern  analytical  methods,  which  prevent  volatilization  and  loss  of 
organic  sulfur  compounds  during  the  combustion,  show  that  plants 
require  larger  amounts  of  sulfur  than  was  formerly  believed  (195). 

Sulfur  in  Animals.  In  1813  Heimich  August  Vogel  published  in  the 
Annales  de  Chimie  et  de  Physique  a  paper  "On  the  existence  of  sulfur  in 
the  bile  and  in  the  blood"  ( 272 ) .  After  Cadet  and  Fourcroy  had  observed 
an  odor  of  hydrogen  sulfide  when  bile  was  treated  with  hydrochloric  acid 
or  distilled,  Vogel  distilled  two  kilograms  of  fresh  ox  bile  from  a  large 
glass  retort  connected  to  a  flask  containing  a  solution  of  lead  acetate.  A 


58  DISCOVERY  OF  THE  ELEMENTS 

small  precipitate  of  lead  sulfide  revealed  the  presence  of  sulfur  in  the 
bile.  He  also  demonstrated  its  presence  in  blood  and  urine  (272).  The 
"Encyclopedic  Methodique"  (1815)  mentioned  its  presence  in  albumen, 
hair,  and  wool  (273). 

CARBON 

That  the  Biblical  word  "coals"  means  charcoal  is  evident  from  the 
proverb  "As  coals  are  to  burning  coals,  and  wood  to  fire;  so  is  a  contentious 
man  to  kindle  strife"  (Prov.  26,  21). 

In  a  discourse  on  the  folly  of  worshipping  a  wooden  idol,  Isaiah  said, 
"And  none  considereth  in  his  heart,  neither  is  there  knowledge  nor  under 
standing  to  say,  I  have  burned  part  of  it  in  the  fire;  yea,  also  I  have  baked 
bread  upon  the  coals  thereof;  I  have  roasted  flesh,  and  eaten  it:  and  shall 
I  make  the  residue  thereof  an  abomination?  shall  I  fall  down  to  the 
stock  of  a  tree?"  (Isa.  44,  19). 


From  Biringuccio's  "Pirotechnia" 
Manufacture  of  Wood  Charcoal 

One  of  the  proverbs  uses  the  figurative  expression  "heaping  coals  of 
fire  on  an  enemy's  head"  to  represent  remorse  caused  by  returning  good 
for  evil:  "If  thine  enemy  be  hungry,  give  him  bread  to  eat;  and  if  he  be 
thirsty,  give  him  water  to  drink:  For  thou  shalt  heap  coals  of  fire  upon 
his  head  .  .  /'  (Prov.  25,  21-2).  In  his  letter  to  the  Christians  in  Rome, 
Paul  urged  them  to  follow  this  precept  .(Rom.  12,  20). 

Carbon  in  the  form  of  lampblack  was  often  mixed  with  olive  oil  or 
balsam  gum  (101,  275)  and  used  as  ink.  It  was  carried  in  an  inkhorn 


ELEMENTS  KNOWN   TO  THE  ANCIENTS  59 

suspended  from  the  girdle,  as  mentioned  by  Ezekiel  six  centuries  before 
Christ:  "And  behold  six  men  came  from  the  way  of  the  higher  gate, 
which  lieth  toward  the  north,  and  every  man  a  slaughter  weapon  in  his 
hand;  and  one  man  among  them  was  clothed  with  linen,  with  a  writer's 
inkhorn  by  his  side  ..."  (Ezek.  9,  2).  Jeremiah,  a  contemporary  of 
Ezekiel,  also  mentioned  ink  (Jer.  36?  18). 

Carbon  in  the  forms  of  charcoal  and  soot  must  certainly  have  been 
known  even  to  prehistoric  races,  and  in  Pliny's  time  the  former  was  made, 
much  as  it  is  today,  by  heating  wood  in  a  pyramid  covered  with  clay  to 
exclude  the  air  (21}.  The  recognition  of  carbon,  the  chief  constituent 
of  charcoal,  as  a  chemical  element,  however,  is  much  more  recent.  In 
an  interesting  article  in  Osiris,  entitled  "The  discovery  of  the  element 
carbon,"  Theodore  A.  Wertime  traced  the  development  of  this  concept 
(276).  In  his  opinion  the  identification  of  carbon  as  an  element  was 
worked  out  step  by  step  by  R.-A.-F.  de  Reaumur,  H.-L.  Duhamel  du 
Monceau,  Torbern  Bergman,  C.  W.  Scheele,  C.-L.  Berthollet,  A.-L. 
Lavoisier,  and  others. 

Reaumur  distinguished  between  steel,  wrought  iron,  and  cast  iron, 
and  stated  that  their  characteristic  properties  "were  related  to  their 
content  of  a  black  combustible  material,  which  he  knew  to  be  the  chief 
constituent  of  charcoal  ..."  (276).  Duhamel  du  Monceau,  who  had 
studied  the  charcoal-making  process,  thought  that  the  "phlogiston"  in  the 
wood  must  be  concentrated  in  the  charring  process.  Bergman  believed 
that  the  essential  differences  between  wrought  iron,  steel,  and  cast  iron 
were  caused  by  a  "plumbago"  (graphite)  precipitate  composed  of  "fixed 
air"  (carbon  dioxide)  and  "phlogiston"*  (276).  Scheele  in  1779  produced 
"fixed  air"  by  burning  graphite  with  saltpeter  and  proved  that  the  constit 
uents  of  graphite  ("plumbago")  are  "aerial  acid  united  with  a  large 
quantity  of  phlogiston,"  or,  as  one  would  say  today,  that  it  consists 
essentially  of  uncombined  carbon  (253,  254).  In  1783-84  Lavoisier 
distinguished  between  hydrogen  and  matter  derived  from  charcoal,  since 
they  form  different  combustion  products  ( water  and  "acide  charbonneux" 
(carbon  dioxide)  respectively).  Berthollet  showed  in  1785  that  methane 
is  formed  from  carbonaceous  matter  and  the  "inflammable  gas  from 
water"  (hydrogen). 

In  1787  Guyton  de  Morveau,  Lavoisier,  Berthollet,  and  Fourcroy 
introduced  in  their  "Methode  de  nomenclature  chimique"  the  terms 
carbone,  for  the  element  carbon,  instead  of  charbon  (charcoal)  and 
"acide  carbonique"  (carbon  dioxide)  instead  of  "air  fixe"  ("fixed  air"). 

*  "Phlogiston"  was  a  hypothetical  principle  supposed  to  escape  with  the  flame  during 
combustion.  See  also  Chapter  7. 


60  DISCOVERY  OF  THE  ELEMENTS 

According  to  the  "Encyclopaedia  Biblica,"  the  word  diamond  as  used 
in  the  old  Testament  probably  does  not  refer  to  the  true  diamond  but 
more  likely  to  corundum  (22,  36).  The  ancient  Hindu  scriptures,  the 
Vedas,  the  Ramayana,  and  the  Mahabharata,  make  frequent  mention  of 
the  diamond. 

In  1694-95  Cosmus  III,  Grand  Duke  of  Tuscany,  made  it  possible 
for  Giuseppe  Averani  and  Cipriano  Antonio  Targioni  of  Florence  to  heat 
a  diamond  with  a  large  burning  glass.  The  gem  was  destroyed  (255). 
Various  modifications  of  this  experiment  were  tried  in  Vienna  and 
Paris  (256). 

P.-J.  Macquer  has  left  us,  in  his  "Dictionary  of  Chemistry/'  a  fine 
first-hand  account  of  the  scientific  history  of  this  gem  (255).  On  July 
26,  1771,  Macquer  and  Godefroy  de  Villetaneuse,  in  presence  of  Jean 
Darcet  (1725-1801),  Hilaire-Marin  Rouelle  (Rouelle  the  Younger),  and 
others,  heated  a  flawless  diamond  in  a  refractory  capsule  in  Macquer's 
wind  furnace.  When  it  reached  the  temperature  of  melting  copper,  a 
flame  could  be  seen  surrounding  it,  and  in  less  than  an  hour  the  gem 
disappeared  without  leaving  a  trace  (257,  258,  259). 

Jewelers  and  diamond  cutters,  however,  were  skeptical.  To  remove 
certain  flaws,  they  had  often  heated  diamonds,  carefully  packed  in  chalk 
dust  and  powdered  charcoal,  and  had  never  experienced  any  loss.  After 
several  inconclusive  experiments  had  been  made  by  others,  Maillard,  a 
famous  gem  cutter,  placed  three  diamonds,  closely  packed  in  charcoal 
dust,  in  the  bowl  of  a  tobacco  pipe,  and  enclosed  it  in  sheet  iron  inside 
a  crucible  filled  with  a  lining  of  chalk  dust  and  a  fusible  sand  used  for 
castings.  After  moistening  the  mixture  with  salt  water  and  letting  it 
dry,  Maillard  heated  the  crucible  in  Macquer's  furnace.  The  contents 
soon  became  so  fluid  that  it  was  necessary  to  allow  the  furnace  to  cool. 

As  Maillard  searched  among  the  ash  and  molten  material  which  had 
fallen  through  the  grate,  the  academicians  were  confident  that  he  would 
never  see  his  diamonds  again.  When  the  airtight,  glassy  covering  was 
broken  away  and  the  crucible  opened,  the  tobacco  pipe,  the  carbon  dust, 
and  the  three  diamonds  were  recovered  intact.  Hence  it  was  evident 
that  both  heat  and  air  were  required  for  the  destruction  of  the  diamond 
(258,  260). 

Pierre-Joseph  Macquer,  a  descendant  of  the  Scottish  nobility,  was 
born  in  Paris  in  1718.  Although  he  chose  medicine  as  his  profession,  he 
devoted  much  time  and  thought  to  physical  science,  especially  to  chem 
istry.  His  "Dictionary  of  Chemistry"  gives  a  comprehensive,  scholarly, 
impartial  view  of  all  branches  of  eighteenth-century  chemical  technology. 
In  his  eulogy,  Condorcet  said,  "The  spirit  one  observes  in  the  works  of 
M.  Macquer  is  the  same  which  directed  his  conduct.  Everything  about 


ELEMENTS  KNOWN  TO  THE   ANCIENTS  61 


Frontispiece  to  the  German  translation  of 
P.-J.  Macquer's  "Dictionnaire  de  Chymie,"  1788 


62  DISCOVERY  OF  THE  ELEMENTS 

him  was  in  harmony;  that  precision  of  meaning,  that  moderation  in  his 
judgments,  that  reserve  in  his  assertions  was  the  source  of  the  modesty, 
tranquility,  and  kindness  which  he  constantly  showed  in  all  the  circum 
stances  of  his  life  .  .  ."  (261). 

In  1772-73  Lavoisier,  Macquer,  Cadet,  and  Mathurin-Jacques  Bris- 
son  ignited  a  diamond  under  a  bell  jar  by  means  of  the  great  Tschirn- 
hausen  burning  glass,  collected  the  resulting  gas  over  mercury,  added 
lime  water,  and  obtained  a  white  precipitate  of  calcium  carbonate  which 
proved  that  the  gas  must  be  carbon  dioxide  (255).  According  to 
Macquer,  many  of  these  experiments  were  carried  out  by  Lavoisier  alone 
and  at  his  own  expense.  "This  enthusiastic  academician,"  said  he, 
"gradually  conceived  several  arrangements  of  crystal  glass  vessels  ..." 
and  finally  used  "glass  bell  jars  inverted  over  dishes,  some  of  which  were 
filled  with  water,  others  with  mercury,  which,  upon  removal  of  the  air, 
was  allowed  to  rise  to  a  certain  height  under  the  bell  jar.  The  diamonds 
were  laid,  uncovered,  on  supports  of  hard  unglazed  porcelain  under  the 
bell  jars,  and  could  thus  be  subjected  to  the  ignition  point  without 
communicating  with  the  outer  air"  (255).  The  details  are  given  in  the 
second  part  of  Lavoisier's  physical  and  chemical  researches  ( 23,  262 ) . 

In  1799  Guy  ton  de  Morveau  converted  the  diamond  first  into  graphite 
and  finally  into  carbonic  acid  (carbon  dioxide).  He  did  not  realize, 
however,  that  graphite  is  merely  another  allotropic  form  of  carbon,  but 
regarded  it  as  partially  oxidized  carbon  (263,  264). 

In  1796  Smithson  Tennant  Droved  that  equal  weights  of  carbon  and 
diamond,  when  burned  with  saltpeter,  yielded  equal  amounts  of  carbon 
dioxide  (258,  265).  Three  years  later  Guyton  de  Morveau  and  Louis 
Clouet  produced  cast  steel  by  heating  a  907-milligram  diamond  in  a  small 
crucible  of  wrought  iron  (24,  258,  266).  As  early  as  1704  Sir  Isaac  New 
ton  stated  in  his  "Optics"  that  the  diamond  must  be  combustible,  and  in 
1772  Lavoisier  found  this  to  be  true  (23).  The  English  chemist  Smithson 
Tennant  proved  in  1796  that  it  consists  solely  of  carbon  (24).* 

Because  of  the  great  importance  of  carbon  compounds  and  carbo 
naceous  substances  a  special  chapter  will  now  be  devoted  to  them. 


LITERATURE  CITED 

(1 )  WINKLER,  C.,  "Ueber  die  Entdeckung  neuer  Elemente  im  Verlaufe  der  letzten 

fiinfundzwanzig  Jahre,"  Ber.,  30,  13  (Jan.,  1897). 

(2)  BASKERVTJLXE.,  C.,  "The  elements:    Verified  and  unverified/*  Science,,  N.  S.y  19, 

88-100  (Jan.,  1904). 

(3)  RAY,  P.  C.,  "History  of  Hindu  Chemistry,"  2nd  ed.,  Vol.  1,  Chuckervertty, 

Chatterjee  and  Co.,  Calcutta,  1904,  p.  25. 


*  For  a  brief  mention  of  attempts  to  prepare  diamonds  artificially  see  p.  768. 


ELEMENTS  KNOWN   TO  THE   ANCIENTS  63 

(4)  Ex.  20:  23;  Deu.  8:  13;  I  Ki.  20:  3;  Job  31:  24;  Ps.  19:   10;  Prov.  16:   16; 

Isa.  60:  17;  Lam.  4:  1;  Hag.  2:  8;  Zee.  13:  9. 

(5)  PLINY  THE  ELDER,  "Natural  History,"  translated  by  Bostock  and  Riley,  Geo. 

Bell  and  Sons,  London,  1856,  Book  XXXIII,  Chap.  21. 

(6)  Ibid.,  Book  XXXIII,  Chap.  32. 

(7)  Genesis,  23:  16. 

(8)  JAGNAUX,  R.,  "Histoire  de  la  Chimie/'  Vol.  2,  Baudry  et  Cie.,  Paris,  1891, 

p.  372. 

(9)  THOMSON,  THOMAS,  "History  of  Chemistry/'  Vol.  1,  Colburn  and  Bentley, 

London,  1830,  p.  53;  E.  O.  VON  LIPPMANN,  "Entstehung  und  Ausbreitung 
der  Alchemic,"  Springer,  Berlin,  1919.,  pp.  519-30. 

(10)  STILLMAN,  J.  M.,  "The  Story  of  Early  Chemistry,"  D.  Appleton  and  Co,,  New 

York  City,  1924  pp.  2-7. 

(11)  Ezra,  8:  27. 

(12)  PLINY  THE  ELDER,  "Natural  History/'  ref.  (5),  Book  XXXIV,  Chap.  39. 

(13)  Job  19:  23-4. 

(14)  Deu.  3:  11. 

(15)  Eze.  27:  12. 

(16)  PLINY  THE  ELDER,  "Natural  History,"  ref.  (5),  Book  XXXIV,  Chap,  47. 

(17)  Ibid.,  Book  XXXIV,  Chap.  48. 

(18)  JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  ref.  (8),  Vol.  2,  p.  366. 

(19)  THOMSON,  THOMAS,  "History  of  Chemistry,"  ref.  (9),  Vol.  1,  p.  103;  PLINY 

THE  ELDER,  "Natural  History,"  ref.  (5),  Book  XXXV,  Chap.  50. 

(20)  JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  ref.  (8),  Vol.  1,  p.  458. 

(21)  Ibid.,  Vol.  1,  p.  680;  PLINY  THE  ELDER,  "Natural  History,"  ref.   (5),  Book 

XVI,  Chap.  8. 

(22)  Ex.  28:  18;  39:  11;  Eze.  28:  13;  Jer.  17:  1. 

(23)  JAGNAUX,  R.,  "Histoire  de  la  Chimie/'  ref.  (S),  Vol.  1,  pp.  664-8;  ERNST  VON 

MEYER,  "Geschichte  der  Chemie/'  4th  ed.,  Veit  and  Co.,  Leipzig,   1914, 
p.  371. 

(24)  THOMSON,  THOMAS,  "History  of  Chemistry,"  ref.  (9),  Vol.  2,  p.  236. 

(25)  BERTHELOT,  P.-E.-M.,  "Les  Origines  de  1'Alchimie,"  Steinheil,  Paris,   1885, 

pp.  227-28. 

(26)  BILLINGER,  R.  D.,  "Assaying  with  Agricola,"  ].  Chem.  Educ.,  6,  349-54  (Feb., 

1929). 

(27)  BERTHELOT,    P.-E.-M.,    "La   Chimie   au    Moyen   Age/'   Vol.    1,    Imprimerie 

Nationale,  Paris,  1893,  p.  364. 

(28)  DE  GALVEZ-CANERO,  A.,  "La  Metalurgia  de  la  Plata  y  del  Mercuric.    Bosquejo 

Historico,"  IX  Congreso  Internacional  de  Ouimica  Pura  y  Aplicada,  Madrid 
1934,  37  pp. 

(29)  PARTINGTON,  J.  R.,  "Origins  and  Development  of  Applied  Chemistry/'  Long 

mans,  Green  and  Co.,  London,  1935,  pp.  14-100;  see  also  HERMANN,  PAUL, 
"Conquest  by  Man/'  Harper,  New  York,  1954,  pp.  51-61. 

(30)  DAVY,  J.,  "The  Collected  Works  of  Sir  Humphry  Davy,  Bart,/'  Smith,  Elder 

and  Co.,  London,  1840?  Vol.  5,  pp.  73,  160-8,  216-20,  310-11. 

(31)  KOPP,  H.,  "Geschichte  der  Chemie/'  Fr.  Vieweg  und  Sohn,  Braunschweig, 

1847,  Vol.  3,  pp.  310-11. 

(32)  GAY-LUSSAC,   L.-J.   and  L.-J.   THENARD,   "En   reponse   aux  recherches   ana- 

lytiques  de  M.  Davy,  sur  la  nature  du  soufre  et  du  phosphore,"  Ann.  chim. 
phys.,  (12,  73,  229-53  (Mar.  31,  1810).    Read  Sept.  18,  1809. 

(33)  DAVY,  H.,  "Sur  la  nature  de  certains  corps,  particulierement  des  alcalis,  du 

soufre,  du  phosphore,  du  carbone  et  des  acides  reputes  simples/'  ibid.,  ( 1 ) 
73,  5-11  (Jan.  31,  1810). 

(34)  HOLMYARD,  E.  J.,  "The  Works  of  Geber  Englished  by  Richard  Russell,  1678/' 

J.  M.  Dent  and  Sons,  London  and  Toronto,  1928,  p.  209. 

(35)  BUGGE,  G.,  "Das  Buch  der  grossen  Chemiker,"  Verlag  Chemie,  Berlin,  1929, 

Vol.  1,  pp.  18-31,  60-9.    Articles  on  Jabir  and  Pseudo-Geber  by  J.  Ruska. 


64  DISCOVERY  OF  THE  ELEMENTS 

(86)     CHEYNE,  T.  K.  and  J.  S.  BLACK,  "Encyclopaedia  Biblica,"  The  Macmillan 
Company,  New  York,  1899,  Vol.  1,  columns  1097-8. 

(37)  SMITH,  J.  M.  P.  and  E.  J.  GOODSPEED,  "The  Bible.    An  American  Translation," 

University  of  Chicago  Press,  Chicago.  1931,  418  pp.  Translation  of  Deu 
teronomy  by  T.  J.  Meek. 

(38)  WEEKS,  M.  E.,  "An  exhibit  of  chemical  substances  mentioned  in  the  Bible," 

J.  Chem.  Educ.,  20,  63-76  (Feb.,  1943). 

(39)  DANA,  J.  D.,  "Manual  of  Mineralogy  and  Lithology,"  John  Wiley  and  Sons, 

New  York,  1880,  3rd  ed.,  p.  144. 
(40}     BROWNE,  C.  A.,  "The  chemical  industries  of  the  American  aborigines,"  Isis, 

23  (2),  417  (Sept.,  1935). 

(41 )  BERGS0E,  PAUL,  "The  Gilding  Process  and  the  Metallurgy  of  Copper  and  Lead 

among  the  pre-Columbian  Indians,"  Danmarks  Naturvidenskabelige  Sam- 
fund,  Copenhagen,  1938,  Ingeni0rvidenskabelige  Skrifter,  No.  A  46,  56  pp. 

(42)  HAMMOND,  G.  P.  and  AGAPITO  REY,  "Narratives  of  the  Coronado  Expedition, 

1540-1542,"  University  of  New  Mexico  Press,  Albuquerque,  1940,  p.  188. 

(43)  WINSHIP,  G.  P.,  "The  Coronado  Expedition,   1540-1542,"  U.   S.  Bu.  Am. 

Ethnology,  Washington,  D.  C.,  1896,  pp.  345,  350,  397,  405,  509,  577,  582. 

(44)  BRERETON,  JOHN,  "A  Brief e  and  True  Relation  of  the  Discouerie  of  the  North 

Part  of  Virginia,"  George  Bishop,  London,  1602,  p.  9. 

(45)  DE  ACOSTA,  FATHER  JOSE,  "Natural  and  Moral  History  of  the  Indies,"  The 

Hakluyt  Society,  London,  1880,  Vol.  1,  pp.  186-211,  223. 

(46)  BARBA,  A.  A.,  "El  Arte  de  los  Metales,"  John  Wiley  and  Sons,  New  York, 

1923,  pp.  67-9.  English  translation  by  R.  E.  Douglass  and  E.  P.  Mathew- 
son. 

(47)  MORGAN,  M.   H.,  "Vitruvius.     The  Ten  Books   on  Architecture,"   Harvard 

University  Press,  Cambridge,  1914,  pp.  215-16. 

(48)  ISSEROW,  SAUL  and  HUGO  ZAHND,  "Chemical  knowledge  in  the  Old  Testa 

ment,"  J.  Chem.  Educ.,  20,  327-35  (July,  1943);  ZAHND,  H.,  and  DOROTHY 
GILLIS,  "Chemical  knowledge  in  the  New  Testament,"  ibid.,  23,  90-7 
(Feb.,  1946);  23,  128-34  (Mar.,  1946). 

(49)  CALEY,  E.  R.,  "Mercury  and  its  compounds  in  ancient  times,"  ibid.,  5,  419- 

24  (Apr.,  1928). 

(50)  GELLERT,  C.  E.,  "Metallurgic  Chemistry,"  T.  Becket,  London,  1776,  p.  57. 

(51 )  VON  LIPPMANN,  E.  O.,  ref.  (9),  vol.  1,  pp.  600-7. 

(52)  SCHELENZ,  H.,  "Geschichte  der  Pharmazie,"  J.  Springer,  Berlin,  1904,  p.  41. 

(53)  HILL,   JOHN,   "Theophrastus's   History   of  Stones,"   printed   for  the   author, 

London,  1774,  2nd  ed.,  pp.  227-35. 

(54)  KOPP,  H.,  ref.  (31),  Vol.  4,  p.  172. 

(55)  MARTIN,   BENJAMIN,  "Biographia  Philosophica,"  W.   Owen,   London,   1764, 

pp.  58-60.     Biographical  sketch  of  Theophrastus. 

(56)  GUNTHER,  R.  T.,  "The  Greek  Herbal  of  Dioscorides,"  Oxford  University  Press 

Oxford,  1934,  pp.  623-6,  638,  648. 

(57)  DAVIS,  TENNEY  L,,  "Remarks  on  the  value  of  historical  studies,"  Report  of 

New  England  Assoc.  of  Chem.  Teachers,  May,  1930,  p.  5. 

(58)  HOPPENSACK,  J.   M.,  "Ueber  den  Bergbau  in  Spanien  iiberhaupt  und  der 

Quecksilver-bergbau  zu  Almaden,"  Weimar,  1796,  158  pp.  Review  in 
Ann.  chim.  phys.,  (1),  25,  51-60  (1798). 

(59)  DE  ACOSTA,  FATHER  JOSE,  ref.  (45),  Vol.  1,  pp.  185,  214-17.    English  trans 

lation  by  Edward  Grimston,  1604. 

(60)  AREVALO,  CELSO,  "La  Historia  Natural  en  Espafia,"  Union  Poligrafica,  Madrid, 

1935,  pp.  143-9. 

(61)  HAWLEY,  C.  E.,  "Notes  on  the  quicksilver  mine  of  Santa  Barbara  in  Peru," 

Am.  J.  Set.,  (2),  45,  5-9  (Jan.,  1868);  "Notes  on  the  quicksilver  mines  of 
Almaden,  Spain,"  ibid.,  (2),  45,  9-13  (1868). 


ELEMENTS  KNOWN  TO  THE  ANCIENTS  65 

(62)  SAGLIO,    E.    and    E.    POTTIER,    "Dictionnaire    des    Antiquites    Grecques    et 

Romames,"  Librairie  Hachette  et  Cie.,  Paris,  1877,  Vol.  4,  pp.  1457-64. 
Article  on  Stannum  by  Maurice  Besnier. 

(63)  BAILEY,  K.  C.,  "The  Elder  Pliny's  Chapters  on  Chemical  Subjects,"  Edward 

Arnold  and  Co.,  London,  1929,  Part  1,  p.  129. 

(64)  BINGHAM,  HIRAM,  "Machu  Picchu,  a  Citadel  of  the  Incas,"  Yale  University 

Press,  New  Haven,  Conn.,  1930,  p.  197. 

(65)  LUCAS,  A.,  "Ancient  Egyptian  Materials  and  Industries/7  Edward  Arnold  and 

Co.,  London,  1934,  2nd  ed.,  pp.  209-11,  214,  352. 

(66)  "The  Complete  Works  of  Homer,"  Modern  Library,  New  York,  no  date,  pp. 

350-4.    The  "Iliad,"  Book  18. 

(67)  RAWLINSON,  G.  and  M.  KOMROFF,  "The  History  of  Herodotus/'  Tudor  Pub 

lishing  Co.,  New  York,  1941,  p.  188;  Book  III  of  the  Herodotus  History. 

(68)  JENKIN,  A.  K.  H.,  "The  Cornish  Miner/'  George  Allen  and  Unwin,  Ltd., 

London,  1927,  351  pp. 

(69)  LODGE,  H.  C.  and  F.  W.  HALSEY,  "The  Best  of  the  World's  Classics/*  Funk 

and  Wagnalls  Co.,  New  York  and  London,  1909,  Vol.  2,  p.  65. 

(70)  HARRAR,  N.  J.,  "Sulfur  from  Popocatepetl,"  J.  Chem.  Educ.,  11,  641  (Dec., 

1934). 

( 71 )  MAcNurr,  F.  A.,  "Letters  of  Cortes/'  G.  P.  Putnam's  Sons,  New  York  and 

London,  1908,  Vol.  2,  p.  204.    Letter  of  Cortes  to  Charles  V,  Oct.  15,  1524. 

(72)  "The  Complete  Works  of  Homer/'  ref.  (66),  pp.  352-3.     Book  XXII  of  the 

"Odyssey." 

(73)  BAILEY,  K.  C.,  ref.  (63),  Vol.  2,  pp.  97-9;  Pliny,  "Historia  Naturalis,"  Book 

35,  paragraphs  174^-7. 

( 74 )  TESTI,  Gusro,  "La  chimica  dello  zolf  o  in  un  poema  del  1759,"  La  Chimica  nell' 

Industria,  nell'  Agricoltura,  e  nella  Biologia,  6,  182-5  (May  31,  1930). 

( 75 )  PINKERTON,  JOHN,  "A  General  Collection  of  the  Best  and  Most  Interesting 

Voyages  and  Travels  in  All  Parts  of  the  World,"  Longman,  Hurst,  Rees,  and 
Orme,  London,  1809,  Vol.  5,  pp.  139-40.  L.  Spallanzanfs  "Travels  in  the 
two  Sicilies." 

( 76 )  MACNUTT,  F.  A.,  ref.  ( 71 ) ,  Vol.  2,  p.  205. 

(77)  WAINWRIGHT,  G.  A.,  "The  coming  of  iron,"  Antiquity,   10,  5-24    (March, 

1936). 

(78)  NININGER,  H.  H.,  "Our  Stone-pelted  Planet,"  Houghton  Mifflin  Co.,  Boston 

and  New  York,  1933,  237  pp. 

(79)  COGHLAN,  H.  H.,  "Prehistoric  iron  prior  to  the  dispersion  of  the  Hittite  Em 

pire,"  Man,  41,  74-80  (July,  Aug.,  1941). 

(80)  CLINE,  WALTER,  "Mining  and  Metallurgy  in  Negro  Africa,"  George  Banta 

Publishing  Co.,  Menasha,  Wis.,  1937,  pp.  17-23.  Chapter  on  Negro  iron- 
working  in  antiquity. 

(81)  CRONSTEDT,  A.  F.,  "Aminnelsetal  ofver  H.  T.  SchefFer,"  Lars  Salvius,  Stock 

holm,  1760,  pp.  15-31. 

(82)  MENSCHUTKIN,  B.  N.,  "Historical  development  of  the  conception  of  chemical 

elements,"  J.  Chem.  Educ.,  14,  59-61  (Feb.,  1937). 

(83)  URDANG,  GEORGE,  "The  early  chemical  and  pharmaceutical  history  of  cal 

omel,"  Chymia,  1,  93-108  (1948). 

( 84 )  DAVIS,  T.  L.,  "Boyle's  conception  of  element  compared  with  that  of  Lavoisier/' 

Isis,  48,  82-91  (July,  1931);  BOYLE  ROBERT,  "The  Sceptical  Chymist," 
1st  ed.,  London,  1661,  p.  350;  LAVOISIER,  A.-L.,  "Trait6  elementaire  de 
chimie,"  1st  ed.,  Paris,  1789,  p.  4. 

(85)  PARTINGTON,   J.   R.,   "The   concepts   of   substance   and   chemical   element/' 

Chymia,  1,  109-21  (1948). 

(86)  FALLOWS,  "The  Popular  and  Critical  Bible  Encyclopedia,"  Howard-Sever 

ance  Co.,  Chicago,  111.,  1907,  Vol.  1,  p.  309. 


66  DISCOVERY  OF  THE  ELEMENTS 

(87)  BHAGVAT,  R.   N.,   "Knowledge  of  the  metals  in  ancient  India/'  /.   Chem. 

Educ.,  10,  659-66  (Nov.,  1933);  see  also  RAY,  P.  R.,  "Chemistry  in  ancient 
India,"  ibid.,  25,  327-35  (June,  1948). 

(88)  "A  Biblia  Sagrada,  contendo  o  Velho  e  o  Novo  Testamento  traduzida  segundo 

os  originaes  hebraico  e  grego.  Tradticgao  Brazileira,"  Am.  Bible  Soc., 
New  York. 

(89)  GLUECK,    NELSON,    "Explorations   in   Eastern   Palestine.      II,"   Annual   Am. 

Schools  of  Oriental  Research,  15,  1-202  (1934-35). 

(90)  PINKERTON,  ref.  (75),  Vol.  10,  p.  199.     C.  Niebuhr's  "Travels  in  Arabia/' 

(91)  "La  Santa  Biblia   .    .    .   traducida  de  las  lenguas  originales  y  cotejada  dili- 

gentemente  con  muchas  y  diversas  traducciones,"  Am.  Bible  Soc.,  New 
York,  1246  pp. 

(92)  NAPIER,  JAMES,  "Manufacturing  Arts  in  Ancient  Times  with  Special  Refer 

ence  to  Bible  History,"  Hamilton,  Adams,  and  Co.,  London,  1874,  362  pp. 

(93)  STEPHEN,  SIR  LESLIE,  and  SIR  SIDNEY  LEE,  "Dictionary  of  national  biog 

raphy,"  Oxford  University  Press,  1921-22,  Vol.  4,  p.  59.  Sketch  of  James 
Napier. 

(94)  "The  Holy  Bible  translated  from  the  Latin  Vulgate    (diligently  compared 

with  the  Hebrew,  Greek,  and  other  editions,  in  various  languages)  .  .  . 
with  annotations  by  the  Rev.  Dr.  Challoner,"  D.  and  J.  Sadlier  and  Co., 
New  York  and  Montreal. 

(95)  HASTINGS,  JAMES,  "Dictionary  of  the  Bible,"  Charles  Scribner's  Sons,  New 

York,  1929,  pp.  619-20.     Article  on  Mining  and  Metals  by  James  Patrick. 

(96)  SCHWARZ,  JOSEPH,  "A  Descriptive  Geography  of  Palestine,"  A.  Hart,  Phila 

delphia,  1850,  pp.  318-24. 

(97)  SINGER,  ISIDORE,  "The  Jewish  Encyclopedia,"  Funk  and  Wagnalls  Co.,  1905, 

Vol.  4,  pp.  260-1.    Article  on  Copper  by  William  Nowack. 

(98)  HILL,   SIR   GEORGE,   "A  history   of   Cyprus,"   University   Press,   Cambridge, 

England,  1940,  Vol.  1,  pp.  8-9,  82. 

(99)  PINKERTON,  ref.  (75),  Vol.  10,  pp.  586-7.    R.  Pococke's  "Travels  in  the  East." 

(100)  LEICESTER,  HENRY  M.,  "The  New  Almaden  Mine.    The  first  chemical  indus 

try  in  California,"  /.  Chem.  Educ.,  20,  235-8  ( May,  1943 ) . 

(101)  "The  Jewish  Encyclopedia,"  ref.   (97),  Vol.  6,  p.  585.     Article  on  Ink  by 

W.  Nowack. 

( 102 )  KOPP,  HERMANN,  ref.  (31),  Part  1,  pp.  27-31. 

(103)  BOAS,  MARIE,  "An  early  version  of  Boyle's  Sceptical  Chymist,"  Isis,  45,  153- 

68  (July,  1954). 

(104)  BROWNE,  C.  A.,  "Alexander  von  Humboldt  as  historian  of  science  in  Latin 

America,"  ibid.,  35,  134-9  (Spring,  1944). 

(105)  BOAS,  MARIE,  "Boyle  as  a  theoretical  scientist,"  ibid,  41,  261-8  (Dec.,  1950). 

(106)  BERGS0E,  PAUL,  "The  metallurgy  and  technology  of  gold  and  platinum  among 

the  Pre-Columbian  Indians,"  Danmarks  Naturvidenskabelige  Samfund, 
Copenhagen,  1937,  44  pp. 

(107)  MAJOR,   R.    H.    "Select   Letters   of   Christopher    Columbus,"   Hakluyt    Soc., 

London,  1870,  2nd  ed.,  pp.  5-7,  55,  57,  201-3. 

(108)  AITON,   A.   S.,   and   L.   C.   KARPINSKI,   "Chronology   of   events   of   scientific 

importance  in  North  and  South  America  in  the  sixteenth  century," 
Archeion,  22,  382-97  (1940). 

(109)  AREVALO,  CELSO,  ref.  (60),  pp.  57-92. 

(110)  "Hakluytus  Posthumus  or  Purchas  his  pilgrimes,"  James  MacLehose  and  Sons, 

Glasgow,  1906,  Vol.  15,  pp.  148-53.  Extracts  from  Oviedo's  "Summarie 
and  generall  historic  of  the  Indies." 

(111)  Ibid.,  Vol.  17,  p.  432. 

(112)  Ibid.,  Vol.  17,  p.  250. 

(113)  PAOLI,  U.  G.,  TEta  aurea  della  metallurgia  ispanocoloniale,"  Archimo  di 

Storia  della  Scienza  S,  200-2  (Jan.-Apr.,  1927). 


ELEMENTS  KNOWN   TO  THE   ANCIENTS  67 

(114)     BARBA,  A.  A.,  ref.  (46),  pp.  64-6. 

(115).     LOTHROP,  S.  K.,  "Gold  ornaments  of  Chavin  style  from  Chongoyape,  Peru/' 
Am.  Antiquity,  6,  250-62  (Jan.,  1941). 

(116)  WALLACE,  JAMES,  "A  Voyage  to  New  Caledonia  in  Darien,"  Phil.  Trans,  and 

Collections  to  the  end  of  the  year  1700  abridged  by  John  Lowthorp, 
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(237)  PAOLI,  U.  G.,  ref.  (113),  pp.  83-94,  200-2. 

(238)  PINKERTON,  JOHN,  ref.   (75),  Vol.  14,  pp.  14-9.     Capt.  Betagh's  "Observa 

tions  on  the  country  of  Peru  and  its  inhabitants,  during  his  captivity." 

(239)  SMITH,  SIR  JAMES  EDWARD,  "A  Selection  of  the  Correspondence  of  Linnaeus 

and  Other  Naturalists,"  Longman,  Hurst,  Rees,  Orme,  and  Brown,  London, 
1821,  Vol.  2,  pp.  506-9. 

(240)  THOMSON,  THOMAS,  "Calomel,"  Annals  of  Philos.,  16,  309-10  (Oct.,  1820). 

(241)  BERGMAN,  T.,  "Schluss  der  Geschichte  von  der  Veremigung  des  Quecksilbers 

mit  Salzsaure,"  Crell's  Neueste  Entdeckungen,  1,  76-82  (1781);  K.  Sven- 
ska  Vet.  Acad.  HandL,  34,  189. 

(242)  BEGUIN,  JEAN,   "Tyrocinium  chymicum,"  Apud  Baleonium,   Venetiis,    1643, 

revised  ed.,  pp.  398-405. 

(248)     SMITH,  F.  PORTER,  "Chinese  chemical  manufactures,"  Am.  Chemist,  4,  56-9 
(Aug.,  1873). 

(244)  RAY,  SIR  P.  C,  ref.  (3),  Vol.  1,  pp.  250-61. 

(245)  DIERGART,  PAUL,  ref.   (235),  pp.  120-6.     Chapter  by  E.  C.  van  Leersum, 

"Preparation  du  calomel  chez  les  anciens  Hindous." 

(246)  Poissonnier,    "Versuche   iiber   frierende   Quecksilber,"    Crell's   Neues   chem. 

Archiv,  8,  176-7  (1791);  Hist.  Acad.  Roy.  des  Sciences  (Paris),  1760, 
P.  49. 

(247)  FRIES,  JAKOB,  "Ueber  das  Gefrieren  des  Quecksilbers  in  freyer  Luft,"  Crell's 

Ann.,  8,  318-23  (1787). 

(248)  MACQUER,  P.-J.,  ref.  (198),  Vol.  5,  pp.  14-5. 

(249)  BAUME,  A.,  "Chymie  experimentale  et  raisonnee,"  P.-F.  Didot  le  jeune,  Paris, 

1773,  Vol.  2,  pp.  395-6. 

(250)  TOURNEFORT,  J.-P.  de,  Ref.  (137),  Vol.  1,  pp.  167-8. 

(251)  "Presentation  of  the  Perkin  Medal  to  Herman  Frasch/'  Met.  Chem.  Eng., 

10,73-82  (Feb.,  1912). 

(252)  "Herman  Frasch,  chemical  engineer,"  Chem.  Eng.  News,  20,  730  (June  10, 

1942). 

(253)  PELLETIER,  CHARLES,  and  SEDILLOT  JEUNE,  "Memoires  et  observations  de 

Bertrand  Pelletier,"  Croullebois,  Fuchs,  etc.,  Paris,1798,  Vol.  1,  pp.  146-58. 

(254)  DOBBIN,  L.,  "The  Collected  Papers  of  C.  W.  Scheele/7  G.  Bell  and  Sons, 

London,  193.1,  pp.  202-7;  Scheele,  K.  Vet.  Acad.  HandL,  40,  238-45 
(1779). 


72  DISCOVERY  OF  THE  ELEMENTS 

(255)  MACQUER,  P.-J.,  Ref.  (198),  Vol.  2,  pp.  14-49. 

(256)  "Wortliche  Erzahlung  der  Versuche,  welche  die  Herren  Darcet  und  RoueTIe 

in  der  chemischen  Werkstatte  des  letztern  mit  Diamanten  und  Edelsteineri 
angestellt  haben,"  Crell's  Neueste  Entdeckungen  in  der  Chemie,  8,  242-50 
(1783);  Roziers  Observations  sur  la  physique,  etc.  4,  (1),  131-58  (1772) 

(257)  BAUME,  A.,  Ref.  (249),  Vol.  1,  pp.  106-16. 

(258)  KOBELL,  FRANZ  VON,  Ref.  (177),  pp.  388-94. 

(259)  D'ARCET   and   ROUELLE,   "Neue   Erfahrungen  'iiber   die   Zerstorbarkeit   des 

Diamants  in  verschlossenen  Gefassen,"  Crell's  Beytrdge  zu  den  Chem. 
Ann.,  1,  part  2,  114-26  ( 1786);  J.  de  Med.,  39,  50  (Jan.-June,  1772). 

(260)  COLEBY,  L.  J.  M.5  "The  Chemical  Studies  of  P.-J.  Macquer,"  George  Allen 

and  Unwin,  Ltd.,  London,  1938,  pp.  74-8. 

(261)  O'CONNOR,    A.    CONDORCET,   and  M.-F.   ARAGO,   "Oeuvres   de   Condorcet," 

Firmin  Didot  Freres,  Paris,  1847,  pp.  125-38.    Eulogy  of  Macquer. 

(262)  LAVOISIER,   "Premier  memoire  sur  la  destruction  du  diamant  par  le  feu," 

Mem.  Acad.  des  Sci.,  1772,  Part  II,  p.  564;  "Seconde  Memoire  .  .  .,"  ibid,, 
1772,  Part  II,  p.  591;  "Oeuvres  de  Lavoisier,"  Imprimerie  Imperiale,  Paris, 
1864,  Vol.  2,  p.  38. 

(263)  BRISSON,  M.  J.,  "Physical  principles  of  chemistry,"  J.  Cuthell  and  Vernor  and 

Hood,  London,  1801,  pp.  180-1. 

(264)  GUYTON  DE  MORVEAU,  "Sur  le  passage  du  diamant  a  1'etat  de  charbon  ou 

d'oxide  noir  de  carbone,"  Ann.  chim.  phys.f  (1)  32  (1799).  (30  Ven- 
demiaire,  an  VHP.) 

(265)  KOPP,  H.,  "Geschichte  der  Chemie,"  Ref.  (31),  Part  3,  pp.  288-92;  Part  4, 

p.  79. 

(266)  GUYTON  DE  MORVEAU,  "De  la  conversion  du  fer  doux  en  acier  fondu  par  le 

diamant,"  Ann.  chim.  phys.,  (1),  31,  326-36  (1799).  (30  Fructidor,  an 
VIP.) 

(267)  CLARK,  BLAKE,  "How  the  Bible  is  building  Israel,"  Readers  Digest,   33, 

26-30  (Mar.,  1954). 

(268)  PERROT  and  CHIPIEZ,  "History  of  Art  in  Phoenicia  and  Its  Dependencies," 

Chapman  and  Hall,  London,  1885,  Vol.  2,  pp.  413-14. 

(269)  MURRAY,  JOHN,  "A  System  of  Chemistry,"  William  Creech,  Edinburgh,  1812, 

3rd  ed.,  Vol.  2,  p.  401. 

(270)  Deyeux,  N.,  "Observations  sur  la  physique,  sur  I'histoire  naturelle,  et  sur  les 

arts,"  /.  de  Physique,  17,  241-2  (1781). 

(271)  NORDENSKIOLD,  A.  E.,  "C.  W.  Scheele.    Nachgelassene  Briefe  und  Aufzeich- 

nungen,"  P.  A.  Norstedt  and  Sons,  Stockholm,  1892,  pp.  334-6. 

(272)  VOGEL,  H.  A.,  "Sur  Fexistence  du  soufre  dans  la  bile  et  dans  le  sang,"  Ann. 

chim.  phys.,  (1),  87,  215-7  (Aug.  31,  1813). 

(273)  "Encyclopedic  methodique.     Chimie  et  metallurgie  par  MM.   Fourcroy  et 

Vauquelin,"  Mme.  Veuve  Agasse,  Paris,  1815,  Vol.  6,  p.  173.  Article  on 
Soufre. 

(274)  CUNNINGHAM,  W.  A.,  "Sulfur,"  /.  Chem.  Educ.,  12,  17-23  (Jan.,  1935);  12, 

83-7  (Feb.,  1935). 

(275)  BROWNLEE,  W.  H.,  "Discoveries  in  the  Judean  wilderness,"  Land  Reborn,  5, 

8-10  CDec.,  1954). 

(576)  WERTIME,  T.  A.,  "The  discovery  of  the  element  carbon,"  Osiris,  11,  211-20 

(1954). 

(577)  PEATTIE,  DONALD  and  LOUISE,  "California's  mother  Lode,"  Reader's  Digest, 

33,77-81  (Nov.,  1954). 

(278)     ADAMS,  F.  D.,  "The  Birth  and  Development  of  the  Geological  Sciences," 
Dover  Publications,  Inc.,  New  York,  1954,  pp.  183-95. 


ELEMENTS  KNOWN  TO  THE  ANCIENTS  73 

(279)  "The  Bible  Blueprint  of  the  Holy  Land/'  broadcast  on  "The  Eternal  Light" 

program  Jan.  9,  1955  by  the  National  Broadcasting  Co.;  see  also  E. 
Aschner,  "Israel's  chemical  industry,"  Chem.  Eng.  News,  33,  4316-23  (Oct. 
10,  1955). 

(280)  PROVENZAL,    GIULIO,    "Profili    Bio-Bibliografici    di    Chimici    Italiani.      Sec. 

XV-Sec,  XIX,"  Istituto  Nazionale  Medico  Farmacologico  Serono,  Rome, 
1937,  pp.  55^62. 

(281)  Ibid.,  pp.  153-60. 

(282)  MENSHUTKIN,    B.    N.,    "Russia's    Lomonosov,"    Princeton    University    Press, 

Princeton,  N.  J.,  1952,  pp.  67-9. 

(283)  FARBER,  EDUARD,  "The  color  of  venous  blood,"  Isis,  45,  3-9  (May,  1954). 


Courtesy  H.  S.  van  Klooster 

Jan  Ingenhousz,  1730-1799,  Dutch  physician  and  plant  physi 
ologist.  Court  physician  to  Maria  Theresia  in  Vienna.  He 
showed  that  only  die  green  parts  of  plants  purify  the  atmosphere 
and  that  they  do  so  only  in  sunlight.  See  also  ref.  (56). 


Hence  sable  Coal  his  massy  couch  extends; 
And  stars  of  gold  the  sparkling  pyrite  blends; 
Hence  dull-eyed  Naphtha  pours  his  pitchy  streams, 
And  Jet  uncolourd  drinks  the  solar  beams  .  .  .  (54). 


2 


Carbon  and  some  of  its  compounds 


Since  the  complete  story  of  carbon  would  be  a  history  of  organic 
chemistry,  asphalt,  carbonate  rocks,  alkaline  carbonates,  fuels, 
foods,  plant  and  animal  nutrition,  photosynthesis,  and  respiration, 
the  following  brief  sketch  can  merely  suggest  the  magnitude  of 
the  subject. 


T 

JL  heophrastus  of  Eresus  described  mineral  coal  (probably  lig 
nite)  in  about  320  B.C.  (!}.  M.  E.  Cunnington  stated  that  coal  was 
sometimes  used  as  fuel  in  Great  Britain  during  the  Roman  period  (2). 
It  has  been  mined  in  the  Midland  Area  (Derbyshire  and  Notts)  since 
1257  (53),  and  by  the  beginning  of  the  seventeenth  century  it  had  become 
one  of  England's  important  natural  resources  (3). 

In  the  second  decade  of  the  eighteenth  century,  Dr.  Rosinus  Len- 
tilius  (Linsenbahrdt)  (1657-1733)  discussed  the  occurrences  of  coal. 
"The  best  description  of  coal/'  said  he,  "is  given  by  Friedr.  Hoffmann  (in 
obs.  phys.  chem.  libr.  II.  obs.  24).  He  says  that  these  coals  are  a  loose, 
porous  earth  intimately  penetrated  by  a  large  amount  of  a  subterranean 
resinous  fluid.  Their  principal  constituent  is  the  lesin,  for  when  that  has 
been  lost,  they  no  longer  smoke  and  burn.  .  ."  (4).  He  also  described  the 
destructive  distillation  of  coal. 

Per  Kalm  stated,  in  the  account  of  his  journey  to  North  America  in 
1748-51,  that  "Coals  have  not  yet  been  found  in  Pennsylvania,  but  people 
pretend  to  have  seen  them  higher  up  in  the  country  among  the  natives. 
Many  people,  however,  agree  that  they  are  met  with  in  great  quantity 
more  to  the  north,  near  Cape  Breton"  (5). 

In  1791  a  Pennsylvania  hunter  named  Philip  Ginther  stumbled  over 
an  uprooted  tree  trunk  on  the  summit  of  Sharp  Mountain  near  the  Lehigh 
Valley  and  saw  in  the  loosened  soil  a  black  rock.  Having  heard  of  the 
presence  of  "stone  coal"  in  this  region,  he  gave  the  specimen  to  Colonel 
Jacob  Weiss,  who  lived  near  the  present  site  of  Mauch  Chunk.  After 
mineralogists  of  Philadelphia  had  identified  it  as  anthracite,  Colonel 
Weiss  in  1792  founded  the  Lehigh  Coal  Mine  Company.  Because  of  the 
cheap  and  abundant  supply  of  wood  and  charcoal,  the  lack  of  transporta 
tion  facilities,  and  the  ignorance  of  the  proper  method  of  firing  coal, 

75 


76  DISCOVERY  OF  THE  ELEMENTS 

however,  there  was  little  demand  for  it.  Blacksmiths  in  Schuykill  County 
used  it  successfully,  and  in  1817  Colonel  George  Shoemaker  sent  eight 
or  ten  wagonloads  of  it  to  Philadelphia.  The  Fair-mount  Nail  Works, 
which  received  several  tons  of  it,  spent  an  entire  morning  in  a  vain 
attempt  to  fire  a  furnace  with  it.  "They  raked  it,  and  they  stirred  it  up, 
and  poked  it,  and  blew  tremendously  upon  it  with  blowers."  The  men 
gave  up  hope  and  went  to  eat  their  dinner.  "Returning  at  the  usual  time, 
their  consternation  may  be  imagined  as  they  beheld  the  furnace-door 
red  hot,  and  the  fire  within  seething  and  roaring  like  a  tempest.  .  .  .  Never 
before  had  such  a  fire  been  seen"  (6). 

In  1824  an  anonymous  contributor  to  the  Aesculapian  Register  of 
Philadelphia  wrote  as  follows:  "Much  as  we  are  gratified  with  the  vast 
advantages  which  we  promise  ourselves  by  the  introduction  of  the  Lehigh 
Coal  into  common  use,  we  already  perceive  an  evil  arising  from  it,  which 
it  becomes  necessary  to  counteract.—  Unlike  the  fuel  heretofore  em 
ployed,  its  ashes  afford  no  alkali  that  can  render  them  useful  in  the 
formation  of  soap;  nor  as  yet  have  they  probably  been  sufficiently  tested 
as  a  manure.  Our  streets  have  therefore  become  their  deposit  .  .  ."  (7). 
He  believed  that  until  coal  could  be  sold  at  from  20  to  25  cents  a  bushel, 
it  would  be  unable  to  compete  successfully  with  wood. 

ASPHALT  AND  BITUMEN 

The  inhabitants  of  ancient  Nineveh  used  an  asphaltic  mortar  prepared 
from  partially  evaporated  petroleum  (8).  In  some  translations  of  the 
Old  Testament,  this  substance  is  called  "pitch"  or  "slime."  When  Noah 
built  the  ark,  he  was  told  to  "pitch  it  within  and  without  with  pitch/' 
For  building  the  Tower  of  Babel,  Noah's  descendants  "had  brick  for 
stone,  and  slime  had  they  for  mortar"  (9). 

Herodotus  (484-425  B.C.)  mentioned  the  occurrence  of  many  lumps 
of  bitumen  in  the  River  Is,  a  small  tributary  of  the  Euphrates  (10).  The 
Babylonians  heated  this  bitumen  and  used  it  instead  of  mortar  for 
cementing  together  the  bricks  of  their  walls  and  buildings  ( 11 ) .  Herodo 
tus  also  spoke  of  a  well  near  Susa  (the  Shushan  of  the  Bible)  which 
yielded  bitumen,  salt,  and  oil  (II).  Cornelius  Tacitus,  a  friend  of  Pliny 
the  Younger,  described  the  bitumen  of  the  Dead  Sea  (12).  R.  J.  Forbes 
states  in  his  book  "Bitumen  and  Petroleum  in  Antiquity"  that  the  ancients 
used  tar  and  pitch  for  waterproofing  pottery,  for  caulking  ships,  and  for 
making  torches,  paint  for  roofs  and  walls,  and  lampblack  for  paints  and 
ink  (13). 

"Asphalt,  or  Judaean  bitumen,  also  called  funeral  gum,  amber  of 
Sodom,  mountain  pitch,  or  mummy  balm,  etc.,"  said  A.-F.  de  Fourcroy, 


CARBON  AND  SOME  OF  ITS  COMPOUNDS  77 

"is  a  black,  heavy,  solid,  shining  bitumen.  It  is  found  on  the  waters  of 
the  Asphalt  Lake  or  Dead  Sea  in  Judaea,  near  which  were  the  ancient 
cities  of  Sodom  and  Gomorrah.  The  inhabitants,  inconvenienced  by  the 
odor  of  this  bitumen  which  collects  on  the  waters,  and  encouraged  by  the 
profit  which  they  gained  from  it,  carefully  gathered  it"  (17). 

PETROLEUM 

Petroleum  has  been  exported  from  Persia  since  the  seventh  cen 
tury  A.D.,  and  the  Baku  oil  fields  have  been  well  known  since  the  ninth 
and  tenth  centuries  (14).  When  Marco  Polo  visited  Armenia  in  the 
thirteenth  century,  he  observed  the  thriving  petroleum  industry:  "On 
the  confines  towards  Georgia,"  said  he,  "there  is  a  fountain  from  which 
oil  springs  in  great  abundance,  insomuch  that  a  hundred  shiploads  might 
be  taken  from  it  at  one  time.  This  oil  is  not  good  to  use  with  food, 
but  'tis  good  to  burn,  and  is  also  used  to  anoint  camels  that  have  the 
mange.  People  come  from  vast  distances  to  fetch  it,  for  in  all  the 
countries  round  about  they  have  no  other  oil"  (15). 

One  of  the  early  writers  on  petroleum  was  Geoffroy  the  Elder. 
"There  are  few  Countries,"  said  he,  "in  which  this  oil  is  not  to  be  found. 
In  the  Island  of  Samos,  a  kind  of  it  is  gathered,  called  by  the  Inhabitants 
by  a  Name  which  signifies  Oleum  Terras;  and  it  is  in  great  Esteem  among 
the  Indians.  In  Italy,  near  Modena,  this  Oil  is  gathered  from  Springs 
and  Wells;  and  indeed  this  whole  Dutchy  abounds  with  it,  especially 
at  a  place  called  Frumetto.  The  Inhabitants  dig  Wells  to  the  Depth  of 
thirty  or  forty  Feet,  till  the  oily  Spring  is  found,  and  there  it  is  ahyays 
mixed  with  Water.  The  Wells  dug  at  the  Foot  of  the  Hill  furnish  a 
large  Quantity  of  very  red  Oil;  those  near  the  Top,  a  white  Oil,  but  in 
smaller  Quantities.  There  is  another  Rock  in  the  same  Country,  near 
the  Apennine  Hills,  where  there  is  a  perpetual  Spring  of  Water,  on  which 
this  Oil  swims  of  a  yellow  Colour,  and  in  so  great  Quantities  that  twice 
a  Week  they  gather  six  Pounds  of  it  at  a  time.  .  .  .  Petroleum  easily  takes 
Fire,  and  it  is  the  Custom  in  many  Places  to  burn  it  in  Lamps  instead  of 
common  Oil  .  .  ."  (16).  Geoffroy  also  mentioned  the  presence  of  petro 
leum  near  Beriers,  Brittany,  and  near  Clermont  in  Auvergne. 

Father  Joseph  de  la  Roche,  Recollet  Daillon,  a  French  Jesuit  mis 
sionary,  visited  some  oil  springs  near  Lake  Erie  in  1627  (18).  The 
Jesuit  "Relation  of  1656-57,"  which  was  edited  by  Paul  le  Jeune  and  pub 
lished  in  Paris  in  1658,  states  that  "As  one  approaches  nearer  to  the 
country  of  the  Cats  (Eries),  one  finds  heavy  and  thick  water,  which 
ignites  like  brandy,  and  boils  up  in  bubbles  of  flame  when  fire  is  applied 
to  it.  It  is,  moreover,  so  oily  that  all  our  Savages  use  it  to  anoint  and 


78  DISCOVERY  OF  THE  ELEMENTS 

grease  their  heads  and  their  bodies"  (19).     This  was  probably  the  oil 
spring  at  Cuba,  Allegany  County,  New  York. 

In  1807-09  Fortescue  Cumings  made  a  tour  of  what  was  then 
called  "the  western  country."  Near  Little  Beaver  on  the  Ohio  River 
and  on  Oil  Creek,  a  branch  of  the  Allegheny  River,  he  saw  an  oily  sub 
stance  bubbling  up  from  the  surface  of  the  water.  Zadok  Cramer,  a 
Pittsburgh  printer  who  annotated  Cumings's  report,  said  that  to  collect 
the  oil,  "The  place  where  it  is  found  bubbling  up  in  the  creek  is  surrounded 
by  a  wall  or  dam  to  a  narrow  compass,  a  man  takes  a  blanket,  flannel,  or 
other  woollen  cloth,  to  which  the  oil  adheres,  and  spreading  it  over  the 
surface  of  the  enclosed  pond,  presses  it  down  a  little,  then  draws  it  up,  and 
running  the  cloth  through  his  hands,  squeezes  out  the  oil  into  a  vessel 
prepared  for  the  purpose;  thus  twenty  or  thirty  gallons  of  pure  oil  can 
be  obtained  in  two  or  three  days  by  one  man"  (-20). 

In  the  American  Journal  of  Science  for  1833  Benjamin  Silliman  the 
Elder  described  an  oil  spring  in  Allegany  County,  New  York.  "The  Oil 
Spring,  or  fountain,"  said  he,  "rises  in  the  midst  of  a  marshy  ground.  .  .  . 
They  collect  the  petroleum  by  skimming  it  like  cream  from  a  milkpan.  .  .  . 
It  has  then  a  very  foul  appearance  like  very  dirty  tar  or  molasses;  but 
it  is  purified  by  heating  it,  and  straining  it  while  hot  through  flannel  or 
other  woolen  stuff.  It  is  used  by  the  people  of  the  vicinity  for  sprains 
and  rheumatism  and  for  sores  upon  their  horses.  It  is  not  monopolized 
by  anyone,  but  is  carried  away  freely  by  all  who  care  to  collect  it.  .  .  . 
The  history  of  this  spring  is  not  distinctly  known.  The  Indians  were 
well  acquainted  with  it,  and  a  square  mile  around  it  is  still  reserved  for 
the.Senecas  .  .  ."  (8).  Silliman  mentioned  that  petroleum  was  often 
sold  in  the  eastern  states  under  the  name  Seneca  Oil.  He  distilled  off 
the  naphtha  from  some  of  it  and  used  the  distillate  to  preserve  his 
specimens  of  sodium  and  potassium. 

Pioneers  on  the  Santa  Fe  trail  used  petroleum  from  some  of  the 
pools  and  streams  in  Miami  County,  Kansas,  to  grease  the  wheels  of  their 
wagons  (21).  After  surveying  part  of  the  new  townsite  of  Lawrence, 
A.  D.  Searl  went  to  Miami  County  in  1855  and  found  oil  seeping  from  the 
ground  near  the  present  site  of  Paola.  The  first  mention  of  petroleum 
in  a  Kansas  newspaper  was  the  following  item  in  the  Lawrence  Herald 
of  Freedom  for  July  25,  1855:  "We  learn  from  R.  S.  Stevens,  Esq.  that 
a  valuable  petroleum  or  rock  oil  has  been  discovered  some  eight  miles 
northeast  of  Paola.  He  states  that  it  can  be  collected  in  the  amount  of 
several  gallons  daily.  He  had  a  bottle  with  him"  ( 21 ) . 

More  than  thirty  years  before  the  drilling  of  the  first  petroleum  well 
in  Oliio,  borings  for  salt  sometimes  yielded  more  petroleum  than  salt  ( 8 ) . 
Since  there  was  little  demand  for  the  oil,  this  always  led  to  disappoint- 


CARBON  AND  SOME  OF  ITS  COMPOUNDS  79 

ment.  The  first  petroleum  well  in  the  United  States  was  drilled  by  Edwin 
L.  Drake  at  Titusville,  Pennsylvania,  in  1859  (22).  J.  T.  Henry  described 
this  event  in  his  "Early  and  Later  Histoiy  of  Petroleum"  as  follows: 

"Saturday  afternoon,  August  28th,  1859,  as  Mr.  Smith  and  his  boys 
were  about  to  quit  for  the  day,  the  drill  dropped  into  one  of  those 
crevices,  common  alike  in  oil  and  salt  borings,  a  distance  of  about  six 
inches,  making  the  total  depth  of  the  whole  well  69  V2  feet.  They  with 
drew  the  tools,  and  all  went  home  till  Monday  morning.  On  Sunday 
afternoon,  however,  "Uncle  Billy  [Smith]  went  down  to  the  well  to 
reconnoiter,  and  peering  in  could  see  a  fluid  within  eight  or  ten  feet  of 
the  surface.  He  plugged  one  end  of  a  bit  of  a  tin  rain-water  spout,  and 
let  it  down  with  a  string.  He  drew  it  up  filled  with  Petroleum.  That 
night  the  news  reached  the  village,  and  Drake,  when  he  came  down  the 
next  morning,  bright  and  early,  found  the  old  man  and  his  boys  proudly 
guarding  the  spot,  with  several  barrels  of  Petroleum  standing  about 

-  •  -"(8). 

At  the  very  beginning  of  the  twentieth  century,  when  Captain 
Anthony  F.  Lucas  was  drilling  for  oil  near  Beaumont,  Texas,  gas  whistled 
out,  and  twisted  sections  of  pipe  together  with  sand  and  rock  were 
forced  out  by  a  gigantic  geyser  of  oil.  This  enormous  "Spindletop"  gusher 
opened  the  great  oil  era  in  Texas  and  the  Southwest.  The  magazine  Life 
commissioned  the  artist  Alexandra  Hogue  to  paint  this  dramatic  scene 
and  used  the  colorful  painting  as  a  cover  design  (50). 

NATURAL  GAS 

In  400  B.C.,  Ktesias  of  Knidos  mentioned  the  occurrence  of  natural 
gas  in  Karamania,  Asia  Minor.  It  provided  "perpetual  flame"  for  the 
fire- worshippers  and  fuel  for  their  homes  (23). 

The  "Records  of  the  Kingdoms  South  of  Mt.  Hua  (Hua  yang  kuo 
chih)/'  a  work  on  the  local  history  and  geography  of  Szechwan  and 
adjacent  regions  of  China  compiled  in  about  347  A.D.,  mentions  "fire 
wells"  (huo  ching)  which  date  from  the  Han  dynasty  (206  B.C.-24  A.D.) 
and  states  that  the  natural  gas  from  them  was  used  for  the  boiling  of 
salt  brines  and  for  other  purposes  (55). 

In  1783  George  Washington  made  some  experiments  at  Rocky  Hill, 
New  Jersey,  to  test  and  explain  the  popular  belief  that  the  creek  that 
runs  near  the  bottom  of  this  hill  could  be  "set  on  fire."  Thomas  Paine 
wrote  in  his  report  of  these  experiments :  "When  the  mud  at  the  bottom 
was  disturbed  by  the  poles,  the  air  bubbles  rose  fast,  and  I  saw  the  fire 
take  from  Gen.  Washington's  light,  and  descend  from  thence  to  the 
surface  of  the  water,  in  a  similar  manner  as  when  a  lighted  candle  is 


80  DISCOVERY  OF  THE  ELEMENTS 

held  so  as  to  touch  the  smoke  of  a  candle  just  blown  out,  the  smoke  will 
take  fire  and  the  fire  will  descend  and  light  up  the  candle.  This  was 
demonstrative  evidence  that  what  was  called  setting  the  river  on  fire,  was 
setting  the  inflammable  air  on  fire  that  arose  out  of  the  mud  .  .  ."  (51 ). 
Thomas  Paine  referred  to  this  flammable  natural  gas  as  "carburetted 
hydrogen." 

Some  of  the  houses  at  Fredonia,  New  York,  were  lighted  with  natural 
gas  as  early  as  1821  (18).  Mrs.  Almira  Hart  Lincoln  Phelps  mentioned 
in  her  "Familiar  Lectures  on  Chemistry"  that  a  rivulet  running  through 


Almira  Hart  Lincoln  Phelps,  1793- 
1884.  Principal  of  the  Patapsco  Insti 
tute  at  Ellicott's  Mills,  Maryland. 
Author  of  "Familiar  Lectures  on 
Chemistry"  and  "Chemistry  for  Be 
ginners"  and  translator  of  a  French 
dictionary  of  chemistry.  She  was  the 
second  woman  to  be  elected  to  the 
American  Association  for  the  Advance 
ment  of  Science.  See  ref.  (57). 


the  village  of  Fredonia  and  another  brook  near  Portland  Harbor,  both  in 
Chautauqua  County,  New  York,  contained  'light  carburetted  hydrogen 
gas"  (methane),  bubbles  of  which  kept  rising  to  the  surface.  The  houses 
at  Fredonia  and  the  lighthouse  at  Portland  Harbor  were  lighted  with  this 
natural  gas  (24,57), 

The  American  Journal  of  Science  for  1840  described  an  amazing 
phenomenon  caused  by  this  kind  of  gas.  At  West  Town,  Chester  County, 
Pennsylvania,  the  students  of  the  boarding  school  used  to  bathe  in  a 
mill-pond  supplied  by  Chester  Creek.  Rising  from  the  creek  were  count 
less  bubbles  of  gas  from  decaying  leaves  and  wood  (25).  "I  first  visited 
the  place  in  the  year  1834/'  said  Moses  Lockwood.  "Taking  as  apparatus 
a  bell-glass  furnished  with  a  stop-cock  and  a  taper,  and  as  companion  an 
assistant  teacher  .  .  .,  we  proceeded  to  the  pond,  readily  filled  the 


CARBON  AND  SOME  OF  ITS  COMPOUNDS  81 

receiver,  and  fired  the  gas  issuing  from  the  stop-cock.  We  next  proposed 
to  burn  the  bubbles  as  they  arose  from  the  water.  On  stirring  the  leaves, 
the  gas  ascended  in  large  quantities,  affording  an  admirably  successful 
experiment.  No  sooner  was  the  lighted  taper  brought  near  the  surface 
of  the  water,  than  we  found  ourselves  enveloped  in  flames.  .  .  .  We 
however  escaped  with  but  a  slight  scorching"  (25).  The  article  con 
cludes  with  a  sprightly  account  of  how  "Master  Moses  set  the  river  afire" 
in  the  presence  of  the  schoolboys. 

COAL  GAS  AND  GAS  LIGHTING 

In  1618  Jean  Tardin,  a  French  physician,  described  a  "fire  well" 
near  some  bituminous  coal  beds  at  Grenoble.  By  heating  some  of  this 
coal  in  a  closed  vessel,  he  prepared  an  artificial  gas  (26,  27). 

In  the  Philosophical  Transactions  for  1667  one  finds  a  description  by 
Thomas  Shirley  of  "A  Well  and  Earth  in  Lancashire  taking  Fire  by  a 
Candle  approached  to  it."  Shirley  had  visited  this  gas  spring  at  Wigan, 
near  Warrington,  in  1659  and  had  observed  that  it  gave  a  flame  about 
eighteen  inches  high  (28).  He  concluded  that  the  gas  must  consist  of 
"bituminous  or  sulphurous  fumes"  from  coal. 

In  1688  the  Reverend  John  Clayton,  rector  of  Crofton,  at  Wakefield, 
Yorkshire,  wrote  a  letter  to  the  Royal  Society  describing  his  recent  voyage 
to  the  American  colony  of  Virginia  (28,  29).  He  compared  the  thunder 
storms  of  Virginia  "with  some  sulphureous  Spirits  which  I  have  drawn 
from  Coals,  that  I  could  no  way  condense,  yet  were  inflammable,  nay 
would  burn  after  they  had  passed  through  Water,  and  that  seemingly 
fiercer,  if  they  were  not  overpowered  therewith.  I  have  kept  of 
this  Spirit  a  considerable  time  in  bladders,  and  tho'  it  appeared  as 
if  they  were  only  blown  with  the  Air,  yet  if  I  let  it  forth  and  fired 
it  with  a  Match  or  Candle,  it  would  continue  burning  til  all  was 
spent"  (28). 

Clayton's  biographer,  Walter  T.  Layton,  believes  that  the  experi 
ments  referred  to  in  this  letter  were  made  at  Wigan,  Lancashire,  some 
time  before  Clayton  went  to  Virginia  in  1686.  An  account  of  them  was 
published  half  a  century  later  in  the  Philosophical  Transactions  for  1739- 
40  (30).  Clayton  not  only  examined  the  Wigan  gas,  as  Shirley  had  done, 
but  also  obtained  coal  from  the  pits  nearby  and  distilled  it  from  a  retort. 
"At  first  there  came  over  only  Phlegm,  afterwards  a  black  Oil,  and  then 
likewise  a  Spirit  arose,  which  I  could  noways  condense  .  .  ."  (30). 
Finding  that  this  "spirit"  was  flammable,  he  collected  and  preserved  it  in 
bladders.  After  pricking  holes  in  the  bladders,  he  lighted  the  escaping 
gas  (26,31). 


82  DISCOVERY  OF  THE  ELEMENTS 

Stephen  Hales,  George  Dixon,  and  Bishop  Watson  afterward  made 
similar  experiments.  Professor  Minckelers  of  the  University  of  Louvain 
distilled  gas  from  powdered  coal  and  lighted  his  lecture  room  with  it  in 
1784-85  (26).  In  1792  William  Murdock  lighted  his  house  at  Redruth, 
Cornwall,  with  gas  made  by  the  destructive  distillation  of  coal  (28). 

J.  J.  Berzelius  drew  in  his  diary  a  sketch  of  one  of  the  gas  fixtures 
that  he  saw  on  his  visit  to  England  in  1818  (52).  "It  lights  up,"  he  said, 
"far  beyond  anything  I  have  ever  seen  with  wax  light  or  lamps  and  has 
over  lamps  the  invaluable  advantage  that  the  light  is  not  so  sharp  ..." 
(52).  The  diary  is  also  illustrated  with  diagrams  of  Fredrick  Accum's 
gas  works  for  illuminating  the  Royal  Mint  in  London  with  his  "thermo- 
lamp"  (47). 

In  January,  1821,  Thomas  Jarman  of  Bristol,  England,  who  had  re 
cently  seen  gas  lights  demonstrated  at  Yale  College,  wrote  as  follows 
to  Benjamin  Silliman:  "...  The  streets  of  the  city  of  Bristol  .  .  .  were 
lighted  with  lamp  oil  till  about  two  years  ago,  when  a  few  persons  united 
in  forming  a  company  for  supplying  the  city  with  gas  from  pit-coal:  I 
was  one  of  that  company.  .  .  I  have  a  house  in  the  city  ...  in  which 
I  use  six  rooms  and  an  entrance  hall  .  .  .  and  I  burn  the  gas  till  ten 
o'clock  at  night,  for  .£25  a  year:  this  is  nearly  about  what  it  cost  me 
for  candles  before;  but  I  have  an  unvarying  and  brilliant  light  in  every 
room,  without  any  trouble  but  the  turning  of  a  key.  All  the  officers  and 
shops  (or  stores)  in  Bristol,  of  any  respectability,  purchase  the  light 
in  the  same  way.  .  .  It  is  intended,  however,  to  sell  the  gas  by  measure; 
as  some  abuses  have  crept  in  by  individuals  burning  the  gas  longer  than 
they  contract  for:  a  Gas-Meter  has  been  invented.  .  ,  I  forgot  to 
mention  to  you  that  the  charcoal  and  tar  produced  from  the  coal  at  the 
works  are  profitable  to  us  .  .  ."  (32). 

An  anonymous  contributor  to  the  Aesculapian  Register  of  Phila 
delphia  wrote  in  1824:  "So  far  back  as  Nov.  1818,  the  following  notice 
respecting  gas  lights  appeared  in  the  American  Daily  Advertiser:  It 
appears,  from  a  work  recently  published  in  London,  that  between  nine- 
teen  and  twenty  thousand  lamps,  lighted  with  carbonated  [sic]  hydrogen 
gas,  have  been  already  placed  in  many  of  the  principal  streets  of  the 
city.  .  .  The  distance  to  which  the  subterranean  tubes  that  convey  the 
gas  has  already  extended  falls  little  short  of  sixty-five  English  miles'" 
(33).  This  contributor  suggested  that  Philadelphia's  streets  ought  to 
be  lighted  in  the  same  manner,  and  in  1835  that  city  finally  adopted  this 
improved  form  of  lighting  (26). 

Further  information  concerning  the  history  of  gas  lighting  may 
be  found  in  Dr.  C.  A.  Browne's  articles  on  Fredrick  Accum  in  volume  2 
of  the  Journal  of  Chemical  Education  (47). 


CARBON  AND  SOME  OF  ITS  COMPOUNDS  83 

FIRE  DAMP  AND  CHOKE  DAMP 

Although  "fire  damp,"  which  is  mainly  methane,  and  "choke  damp" 
(carbon  dioxide)  are  frequent  causes  of  mine  accidents,  Dr.  William 
Brownrigg  learned  how  to  make  good  use  of  them.  In  1741  he  com 
municated  to  the  Royal  Society  several  papers  on  the  gases  of  coal 
mines,  but  preferred  to  withhold  them  from  publication  until  he  could 
prepare  a  comprehensive  treatise  on  the  subject.  His  laboratory  at 
Whitehaven  was  provided  with  several  gas  furnaces  of  his  own  design 
and  a  constant  supply  of  fire  damp  from  the  nearby  mines.  Because  of 
his  skill  in  foretelling  explosions  by  the  rapid  fall  of  the  barometer, 
mine  operators  often  consulted  him. 

He  also  showed  that  many  mineral  waters  contain  considerable  quan 
tities  of  "air"  identical  with  choke  damp.  Even  at  this  early  date  he 
recognized  the  acidic  nature  of  carbon  dioxide  and  showed  that  some  of 
the  earths  which  had  been  precipitated  from  the  water  could  be  redis- 
solved  by  the  choke  damp.  He  showed  that,  although  "the  air  from 
fermenting  liquors  ...  is  ...  a  deadly  poison  when  applied  to  the 
lungs  .  .  .  exactly  in  the  manner  of  the  choak-damp,  .  .  .  yet  never 
theless  this  air,  when  taken  inwardly  in  a  convenient  quantity  of  a  liquid 
vehicle,  is  found  to  have  wonderfully  exciting  and  reviving  qualities  ..." 
(34) .  For  his  experiments  on  choke  damp  and  carbon  dioxide  Dr.  Brown 
rigg  was  awarded  the  Copley  Medal. 

CARBON  IN  PLANT  AND  ANIMAL  NUTRITION 

Leonardo  da  Vinci  ( 1452-1519 )  knew  that  plants  seek  air  and  light 
and  that  they  can  utilize  even  vitiated  air  (35,  36}.  One  of  the  most 
brilliant  discoveries  of  the  eighteenth  century  was  the  explanation  of  the 
wonderful  role  of  carbon  and  oxygen  in  vegetation.  The  Swiss  entomol 
ogist  Charles  Bonnet  (1720-1793)  observed  gas  bubbles  rising  from  the 
leaves  of  a  grapevine  immersed  in  water  in  the  sunshine.  Since  dead 
leaves  immersed  in  water  containing  air  also  collect  bubbles  on  their 
surface,  he  did  not  understand  the  nature  of  this  gas  nor  recognize 
that  it  resulted  from  a  life  process  within  the  leaves  themselves  (37,  38, 
39). 

As  early  as  1771  Joseph  Priestley  noticed  that  this  process  purified 
the  air,  and  in  1778  he  identified  the  gas  as  "dephlogisticated  air" 
(oxygen)  (40).  "I  have  been  so  happy,"  said  he,  "as  by  accident  to  have 
hit  upon  a  method  of  restoring  air  which  has  been  injured  by  the  burn 
ing  of  candles,  and  to  have  discovered  at  least  one  of  the  restoratives 
which  nature  employs  for  this  purpose.  It  is  vegetation.  .  .  ,  Finding 
that  candles  would  burn  very  well  in  air  in  which  plants  had  grown  a 


84  DISCOVERY  OF  THE  ELEMENTS 

long  time,  and  having  had  some  reason  to  think  that  there  was  some 
thing  attending  vegetation  which  restored  air  that  had  been  injured  by 
respiration,  I  thought  it  was  possible  that  the  same  process  might  also 
restore  the  air  that  had  been  injured  by  the  burning  of  candles.  Accord 
ingly,  on  the  17th  of  August  1771,  I  put  a  sprig  of  mint  into  a  quantity 
of  air  in  which  a  wax  candle  had  burned  out,  and  found  that,  on  the  27th 
of  the  same  month,  another  candle  burned  perfectly  well  in  it.  ...  This 
remarkable  effect  does  not  depend  on  anything  peculiar  to  mint,  which 
was  the  plant  that  I  always  made  use  of  till  July  1772;  for  on  the  16th 
of  that  month  I  found  a  quantity  of  this  kind  of  air  to  be  perfectly 
restored  by  sprigs  of  balm,  which  had  grown  in  it  from  the  7th  of  the 
same  month"  (40}. 

Priestley  took  some  "air  made  thoroughly  noxious  by  mice  breathing 
and  dying  in  it,  and  divided  it  into  two  parts;  one  of  which,"  said  he, 
"I  put  into  a  phial  immersed  in  water;  and  to  the  other  (which  was 
contained  in  a  glass  jar  standing  in  water)  I  put  a  sprig  of  mint.  This 
was  about  the  beginning  of  August,  1771,  and  after  eight  or  nine  days, 
I  found  that  a  mouse  lived  perfectly  well  in  that  part  of  the  air  in 
which  the  sprig  of  mint  had  grown,  but  died  the  moment  it  was  put 
into  the  other  part  of  the  same  original  quantity  of  air;  and  which  I  had 
kept  in  the  very  same  exposure,  but  without  any  plant  growing  in  it" 
(40). 

Priestley  soon  became  interested  in  the  little  bubbles  which  he  saw 
rising  from  the  stalks  and  roots  of  plants  growing  in  water.  "Few  per 
sons,  I  believe,"  said  he,  "have  met  with  so  much  unexpected  good 
success  as  myself  in  the  course  of  my  philosophical  pursuits.  .  .  .  But 
none  of  these  unexpected  discoveries  appear  to  me  to  have  been  so 
extraordinary  as  that  which  I  am  about  to  relate.  ...  In  the  course  of 
my  experiments  on  the  growth  of  plants  in  water  impregnated  with 
fixed  air  [carbon  dioxide],  I  observed  that  bubbles  of  air  seemed  to 
issue  spontaneously  from  the  stalks  and  roots  of  several  of  those  which 
grew  in  the  unimpregnated  water;  and  I  imagined  that  this  air  had 
percolated  through  the  plant.  It  immediately  occurred  to  me  that  if 
this  was  the  case,  the  state  of  that  air  might  possibly  help  to  determine 
what  I  was  at  that  time  investigating,  viz.  whether  the  growth  of  plants 
contributes  to  purify,  or  to  contaminate  the  air  .  .  .  (40). 

Although  Priestley  believed  that  green  plants  always  free  the 
atmosphere  from  "fixed  air"  [carbon  dioxide],  C.  W.  Scheele  thought 
that  they  always  increase  the  amount  of  "fixed  air"  in  the  atmosphere. 
In  a  letter  which  he  wrote  to  J.  G.  Gahn  in  May,  1772,  but  forgot  to 
mail,  Scheele  wrote:  "In  the  assertion  that  Vegetabilia  are  able  to  im 
prove  again  air  which  is  unsuitable  for  respiration,  the  English  experi- 


CARBON  AND  SOME  OF  ITS  COMPOUNDS  85 

menter  has  certainly  gone  astray,  and  the  vessels  in  which  these  plant 
experiments  were  carried  out  not  made  tight,  for  plants  would  scarcely 
grow  in  such  air,  and  insects  die  as  soon  as  they  again  reach  it,  and,  in 
fact,  sooner  than  before"  (41).  From  these  results  it  seems  probable 
that  Priestley's  plants  must  have  been  better  illuminated  than  those  of 
Scheele. 

When  Benjamin  Franklin  saw  some  of  Priestley's  plants  flourishing 
in  <chighly  noxious  air,"  he  expressed  great  satisfaction:  "The  strong 
thriving  state  of  your  mint  in  putrid  air  seems  to  shew  that  the  air  is 
mended  by  taking  something  from  it,  and  not  by  adding  to  it.  ...  I 
hope  this  will  give  some  check  to  the  rage  of  destroying  trees  that  grow 
near  houses,  which  has  accompanied  our  late  improvements  in  gardening, 
from  an  opinion  of  their  being  unwholesome.  I  am  certain,  from  long 
observation,  that  there  is  nothing  unhealthy  in  the  air  of  woods;  for  we 
Americans  have  every  where  our  country  habitations  in  the  midst  of 
woods,  and  no  people  on  earth  enjoy  better  health,  or  are  more  prolific" 
(40). 

In  presenting  the  gold  medal  of  the  Royal  Society  to  Priestley  in 
1773,  Sir  John  Pringle  said  that  "these  experiments  show  us  plainly  that 
no  plant  grows  in  vain,  but  that  every  one  of  them,  from  the  oak  in  the 
forest  to  the  grass  in  the  field,  is  useful  to  mankind.  Even  those  which 
seem  to  have  no  special  use  help  to  keep  the  atmosphere  sufficiently 
pure  for  animal  life"  (37).  With  this  inspiring  thought  in  mind,  Jan 
Ingenhousz  (1730-1799)  began  to  investigate  the  gas  evolved  by  plants. 
In  his  first  paper  on  the  subject,  entitled  "Experiments  upon  vegetables, 
discovering  their  great  power  of  purifying  the  common  air  in  the  sun 
shine  and  of  injuring  it  in  tiie  shade  and  at  night,"  which  was  published 
in  London  in  1779,  he  proved  that  green  plants  exposed  to  daylight  are 
able  to  purify  the  atmosphere  from  the  products  of  animal  respiration. 
He  also  showed  that  both  Priestley  and  Scheele  were  partly  right  and 
partly  in  error,  that  the  green  parts  of  plants  give  off  oxygen  only  in  the 
daylight,  and  that  the  parts  which  are  not  green  (such  as  roots,  flowers, 
and  fruits)  give  off  carbon  dioxide  in  darkness.  Ingenhousz  thus  made 
a  clear  distinction  between  respiration  and  assimilation  in  plants  and 
showed  that  plants  obtain  their  carbon  not  from  the  soil  but  from  the 
atmosphere. 

When  J.-H.  Hassenfratz  maintained  that  the  plant  obtains  its  carbon 
from  the  soil  through  its  roots,  Ingenhousz  replied  that  if  that  were  true 
a  large  tree  could  scarcely  be  expected  to  find  its  food  in  the  same  spot 
for  hundreds  of  years  (38). 

Jan  Ingenhousz  was  born  at  Breda  in  the  Netherlands  on  December 
8?  1730.  In  the  Universities  of  Lpwen?  Leyden?  Paris,  and  Edinburgh  he 


86  DISCOVERY  OF  THE  ELEMENTS 

received  an  unusually  fine  education.  When  at  the  age  of  sixteen  years 
he  sought  permission  to  attend  medical  lectures  at  Lowen,  the  Rector 
expressed  doubt  as  to  whether  so  young  a  boy  could  be  well  enough 
prepared,  especially  in  Greek  and  Latin.  Seeing  a  Greek  version  of  the 
Old  Testament  lying  on  a  table,  Jan  asked  the  Rector  to  select  a  passage 
for  him  to  translate  into  Latin.  To  the  Rector's  astonishment,  the  boy 
translated  it  rapidly  and  correctly  ( 37 ) . 

Ingenhousz  spent  much  of  his  life  in  England  and  Austria.  In  1788 
he  went  to  France,  arrived  in  Paris  on  July  14th  of  that  year,  and  witnessed 
the  fall  of  the  Bastille.  Shocked  by  the  terrible  disorder,  he  left  Paris 
the  following  day,  determined  to  leave  the  European  turmoil  and  work 
peacefully  in  America  with  his  friend  Benjamin  Franklin.  He  first 
returned  to  the  Netherlands,  however,  because  of  the  death  of  his  brother. 
Two  years  later,  while  in  England  awaiting  passage  to  America,  he 
received  news  that  made  him  give  up  forever  all  thought  of  emigrating: 
Benjamin  Franklin  had  died,  and  America  without  Franklin  had  no  more 
charm  for  Jan  Ingenhousz  (37). 

Dr.  Thomas  Young  said  that  Dr.  Ingenhousz  "was  in  the  habit  of 
collecting  the  gas  from  cabbage  leaves  and  of  keeping  it  bottled  up  in 
his  pocket;  and  he  was  prepared  with  some  coils  of  iron  wire  fastened 
into  the  corks,  in  order  to  exhibit  the  brilliant  phenomenon  to  his  friends" 
( 43 ) .  In  developing  these  new  views  of  plant  nutrition,  Ingenhousz  was 
guided  in  his  later  years  by  Lavoisier's  great  discoveries  on  the  nature 
of  combustion  (44). 

In  1782-83  Jean  Senebier  of  Geneva,  Switzerland,  verified  many 
of  Ingenhousz's  results  (39,  45,  46).  When  he  placed  plants  in  the  sun 
shine  in  water  of  high  carbon  dioxide  content,  they  gave  off  more  oxygen 
than  did  plants  grown  in  water  low  in  carbon  dioxide  (35).  He  recog 
nized  also  that  this  abundant  production  of  oxygen  by  the  green  parts 
of  the  plant  was  activated  not  by  heat  but  by  light  ( 35,  48 ) . 

To  stimulate  interest  in  the  experimental  determination  of  the 
different  sources  of  carbon  in  vegetables,  the  National  Institute  of  France 
in  1804  and  1805  offered  a  generous  prize  (49). 

Theodore  de  Saussure  showed  that  when  a  seed  begins  to  germinate 
it  loses  carbon  as  carbon  dioxide.  Jean-Baptiste  Boussingault  (1802- 
1887)  then  studied  a  later  stage  of  germination  of  wheat  and  clover 
(Trifolium  pratense),  and  found  that  the  process  became  more  complex. 
As  the  green  parts  of  the  plants  developed,  a  new  chemical  reaction 
occurred  (42,  45).  "The  action  of  the  green  matter,"  said  Boussingault, 
"begins  to  be  manifested  long  before  the  first  phases  of  germination  have 
entirely  ceased;  so  that  during  a  certain  time  two  opposite  forces  are  at 
work  simultaneously.  One  of  these,  as  we  have  seen,  tends  to  discharge 


CARBON  AND  SOME  OF  ITS  COMPOUNDS  87 

carbon  from  the  seed;  the  other  tends  to  accumulate  this  element  within 
it.  So  long  as  the  first  of  these  forces  predominates,  the  seed  loses  carbon; 
but  with  the  appearance  of  the  green  matter  the  young  plant  recovers  a 
portion  of  this  principle;  finally,  when  by  the  progress  of  the  vegetation 
the  second  force  surpasses  the  first  in  energy,  the  plant  grows,  increases, 
and  advances  to  maturity.  .  .  .  The  presence  of  light  is  indispensable 
to  the  manifestation  of  the  chemical  force  by  which  the  green  parts  of 
plants  appropriate  the  gaseous  elements  of  the  atmosphere.  Germination, 
on  the  contrary,  may  take  place  in  absolute  darkness"  (45}. 

Plants  are  thus  able  to  synthesize  innumerable  carbonaceous  products 
such  as  cellulose,  starch,  sugars,  lignin,  dextrin,  and  gums  (42).  "Plants 
and  animals,"  said  J.-B.  Dumas,  "come  from  the  air  and  return  to  it"  (42). 

LITERATURE  CITED 

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und  der  Technik,"  J.  Springer,  Berlin,  1908,  2nd  ed.,  p.  18. 

(2)  CUNNINGTON,  M.  E.,  "Mineral  coal  in  Roman  Britain/'  Antiquity,  7,  89-90 

(Mar.,  1933);  Gent.  Mag.,  1866  (1),  335;  ibid.,  1857  (1),  625;  ibid.,  1843 
(1),303. 

(3)  MERTON,  R.  K.,  "Science  in  seventeenth-century  England,"  Osiris,  4,  360-632 

(1938). 

(4)  LENTILIUS,   ROSIN,   "Von  den   Steinkohlen,   "Crell's  Neues  chem.   Archiv,   1, 

301-6    (1784);   Abh.   Romisch-Kayserlichen   Akad.    der   Naturforscher,    1, 
235  (1721-25). 

(5)  PINKERTON,  JOHN,  "A  General  Collection  of  the  Best  and  Most  Interesting 

Voyages  and  Travels,"  Longman,  Hurst,  Rees,  and  Orme,  London,   1812, 
Vol.  13,  p.  405.    Per  Kalm's  "Travels  in  North  America." 

(6)  ANON.,  "Coal  and  the  coal  mines  of  Pennsylvania,"  Harper's  Mag.,  15,  451-69 

(Sept.,  1857). 

(7)  "Lehigh  coal,"  Aesculapian  Register  (Philadelphia},  1,  5  (June  17,  1824). 

(8)  HENRY,  J.  T.,  "The  Early  and  Later  History  of  Petroleum,"  James  B.  Rodger, 

Philadelphia,  1873,  pp.  9-12,  20-6,  91,  323-30. 

(9)  Genesis  6:  14;  11:  3. 

(10)  DARMSTAEDTER,  LUDWIG,  Ref.  (1),  p.  11. 

(11)  RAWLINSON,  G.  and  M.  KOMROFF,  "The  History  of  Herodotus,"  Tudor  Pub 

lishing  Co.,  New  York,  1941,  p.  67  (Book  I  of  Herodotus);  ibid.,  p.  262 
(Book  IV);  ibid.,  p.  346  (Book  VI). 

(12)  FYFE,  W.  H.,  "Tacitus.    The  Histories,"  Clarendon  Press,  Oxford,  1912,  Vol.  2, 

pp.  109-10;  Tacitus,  History,  Book  5,  Chapter  6. 

(13)  FORBES,  R.  J.,  "Bitumen  and  Petroleum  in  Antiquity,"  E.  J.  Brill,  Leyden,  1936, 

105  pp. 

(14)  LIPPMANN,  E.  O.  VON,  "Petroleum  im  friihen  Mittelalter,"  Archivio  di  Storia 

della  Scienza,  8,  40-1  (Jan.-Apr.,  1927). 

(15)  PARKS,  G.  B.,  "The  Book  of  Ser  Marco  Polo,  the  Venetian,"  Book  League  of 

America,  New  York,  1930,  p.  25. 

(16)  GEOFFROY,  E.-F.,  "A  Treatise  of  the  Fossil,  Vegetable,  and  Animal  Substances 

That  Are  Made  Use  of  in  Physick,"  W.  Innys,  R.  Manby,  et  al.,  London, 
1736,  pp,  133-5. 

(17)  FOURCROY,  A.-F.  DE,  "Systeme  des  connaissances  chimiques,"  Baudouin,  Paris, 

Brumaire,  an  IX,  1801,  Vol.  8,  pp.  234-56,  241-2. 


88  DISCOVERY  OF  THE  ELEMENTS 

(18)  MILLS,  EDMUND  J.,  "Destructive  Distillation,"  Guraey  and  Jackson,  London, 

1892,  pp.  108-9. 

(19)  THWAITES,  R.  G.,  "Travels  and  Explorations  of  the  Jesuit  Missionaries  in  New 

France,  1610-1791,"  Burrows  Brothers  Co.,  Cleveland,  Ohio,  1899,  Vol.  43, 
pp.  261  and  326. 

(20)  THWAITES,   R.   G.,   "Early  Western  Travels,   1748-1846,"  A.    H.   Clark   Co., 

Cleveland,  Ohio,  1904,  Vol.  4,  pp.  101-2. 

( 21 )  HOWES,  CECIL,  "Kansas  oil  used  by  pioneers  long  before  wells  were  drilled," 

Kansas  City  Times,  Oct.  13,  1938. 

(22)  WILSON,  C.  W.,  "Foundation  and  development  of  the  gas  industry  in  America," 

/.  Chem.  Educ.,  18,  103-7  (March,  1941). 

(23)  DARMSTAEDTER,  LUDWIG,  Ref.  (1),  p.  14. 

(24)  PHELPS,  MRS.  A.  H.  L.,  "Familiar  Lectures  on  Chemistry  for  Schools,  Families, 

and  Private  Students,"  F.  J.  Huntington  and  Co.,  New  York,  1838,  448  pp, 

(25)  LOCKWOOD,    MOSES    B.,    "Carburetted    hydrogen,"    Am.    J.    Sci.,    39,    200-1 

(1840). 

(26)  ROBINS,  F.  W.,  "The  Story  of  the  Lamp  and  the  Candle,"  Oxford  University 

Press,  London,  New  York,  and  Toronto,  1939,  pp.  116-19. 

(27)  TARDIN,  JEAN,  "Histoire  naturelle  de  la  fontaine  qui  brusle  pres  de  Grenoble," 

Tournon,  1618. 

(28)  LAYTON,  W.  T.,  "The  Discoverer  of  Gas  Lighting.    Notes  on  the  life  and  work 

of  the  Rev.  John  Clayton,  D.D.,  1657-1725,"  Walter  King  Ltd.,  London, 
1926,  56  pp. 

(29)  BROWNE,   C.   A.,   "Historical  observations   during   a  recent  chemical  trip   to 

Europe,"  J.  Chem.  Educ.,  17,  57-63  (Feb.,  1940). 

(SO)     CLAYTON,  JOHN,  "An  experiment  concerning  the  spirit  of  coals,"  Phil.  Trans., 
41,  59-61  (1739-40). 

(31)  CLAYTON,  JOHN,  "An  experiment  concerning  the  spirit  of  coals,"  Phil  Trans. 

Abridgment  by  John  Martyn,  9  (3),  395-7  (1747). 

(32)  JARMAN,  THOMAS,  "On  gas  lights,"  Am.  J.  Sci.,  (1),  3,  170-3  (1821). 

(33)  "Gas  lights,"  Aesculapian  Register  (Philadelphia),  1,  37-8   (July  15,  1824). 

(34)  BROWNRIGG,  WILLIAM,  "On  the  uses  of  a  knowledge  of  mineral  exhalations 

when  applied  to  discover  the  principles  and  properties  of  mineral  waters, 
the  nature  of  burning  fountains  and  those  poisonous  lakes  called  averni," 
Phil  Trans.,  55,  218-43  (1765);  ibid.,  64,  357-71  (1774). 

(35)  TRIER,    GEORG,    "Chemie   der   Pflanzenstoffe,"    Verlag   von    Gebriider    Born- 

traeger,  Berlin,  1924,  pp.  11-21. 

(36)  LIPPMANN,   E.    O.   VON,   "Abhandlungen   und   Vortrage   zur   Geschichte    der 

Naturwissenschaften,"  Veit  and  Co.,  Leipzig,  1906,  pp.  361-2,  368. 

(37)  WIESNER,  JULIUS,  "Jan  Ingenhousz.     Sein  Leben  und  sein  Wirken  als  Natur- 

forscher  und  Arzt,"  Carl  Konegen,  Vienna,  1905,  252  pp. 

(38)  SACHS,  JULIUS  VON,  "History  of  Botany,  1530-1860,"  Clarendon  Press,  Oxford, 

1890,  pp.  491-504. 

(39)  FUETER,  EDUARD,  "Grosse  Schweizer  Forscher,"  Atlantis  Verlag,  Zurich,  1939, 

pp.  132-3,  148-9.    Biographical  sketches  of  Bonnet  and  Senebier. 

(40)  PRIESTLEY,   J.,   "Experiments   and   Observations   on  Different   Kinds   of  Air," 

Thomas  Pearson,  Birmingham,  1790,  Vol.  3,  pp.  247-92. 

(41)  NORDENSKIOLD,  A.  E.,  "C.  W.  Scheele.     Nachgelassene  Briefe  und  Aufzeich- 

nungen,"  P.  A.  Norstedt  &  Soner,  Stockholm,  1892,  pp.  100-1. 

(42)  DUMAS,  J.-B.,  and  J.-B.  BOUSSINGAULT,  "Essai  de  statique  chimique  des  £tres 

organises,"  Fortin,  Masson  et  Cie.,  Paris,  1844,  3rd  ed.,  pp.  1-27,  140. 

(43)  PEACOCK,  GEORGE,  "Miscellaneous  Works  of  the  Late  Thomas  Young,"  John 

Murray,  London,  1855,  vol.  2,  pp.  501-4.  Biographical  sketch  of  Jan 
Ingenhousz. 

(44)  Review  of  J.  Wiesner's  "Jan  Ingenhousz.     Sein  Leben  und  sein  Wirken  als 

Naturforscher  und  Arzt,"  Nature,  75,  3-4  (Nov.  1,  1906). 


CARBON  AND  SOME  OF  ITS  COMPOUNDS  89 

(45)  BOUSSINGAULT,  J.-B.,  "Role  of  chlorophyll  in  plants,"  Set.  News  Letter,  13, 

377-8  (June  16,  1928). 

(46)  SENEBIER,  JEAN,  "Memoires  physico-chymiques  sur  Tinfluence  de  la  lumiere 

solaire  pour  modifier  les  etres  des  trois  regnes  de  la  Nature,  et  surtout  ceux 
du  regne  vegetal/'  Barthelemi  Chirol,  Geneva,  1782;  "Recherches  sur 
Hnfluence  de  la  lumiere  solaire  pour  metamorphoser  Tair  fixe  en  air  pur  par 
la  vegetation,"  Geneva,  1783. 

(47)  BROWNE,  C.  A.,  "The  life  and  chemical  services  of  Fredrick  Accum,"  /.  Chem. 

Educ.,  2,  829-51  (Oct.,  1925);  2,  1008-34  (Nov.,  1925);  2,  1140-9  (Dec., 
1925). 

(48)  BAY,  J.  C.,  "Jean  Senebier,  1742-1808,"  Plant  Physiology,  6,  189-93   (Jan., 

1931). 

(49)  "Sources  of  carbon  in  vegetables,"  Nicholsons  J.,  (2),  10,  301  (Apr.,  1805). 

(50)  Life,  Feb.  10,  1941,  p.  41. 

( 51 )  BROWNE,   C.   A.,   "Thomas  Paine's  theory  of  atmospheric  contagion  and  his 

account  of  an  experiment  performed  by  George  Washington  upon  the 
production  of  marsh  gas,"  /.  Chem.  Educ.,  2,  99-101  (Feb.,  1925). 

(52)  SODERBAUM,    H.    G.,    "Jac.    Berzelius    Reseanteckningar,"   P.    A.    Norstedt    & 

Soner,  Stockholm,  1903,  pp.  94-5,  164-8. 

(53)  HART,  IVOR  B.,  "The  Great  Engineers,"  Methuen  &  Co.  Ltd.,  London,  1928, 

pp.  24-6. 

(34)     DARWIN,  ERASMUS,  "A  Botanic  Garden,"  J.  Johnson,  London,  1791,  2nd  ed., 
p.  90. 

(55)  RUDOLPH,  R.  C.,  "A  second-century  Chinese  illustration  of  salt  mining,"  Isis, 

43,  39-41  (Apr.,  1952). 

(56)  VAN  KLOOSTER,  H.  S.,  "Jan  Ingenhousz,"  /.  Chem.  Educ.,  29,  353-5   (July, 

1952). 

(57)  WEEKS,  M,  E.  and  F.  B.  DAINS,  "Mrs.  A.  H.  Lincoln  Phelps  and  her  services  to 

chemical  education,"  /.  Chem.  Educ.,  14,  53-7  (Feb.,  1937). 


Sixteenth-century  cartoon  on  alchemy 


Penotus  [Bernard  Gabriel  Penot]  .  .  .  died  a 
hundred  years  old  wanting  but  two,  .  .  .  and  he 
used  to  say  before  he  died,  having  spent  his  whole 
life  in  vainly  searching  after  the  Philosophers'  stone, 
that  if  he  had  a  mortal  Enemy  he  did  not  dare  to 
encounter  openly,  he  would  advise  him  above  all 
things  to  give  himself  up  to  the  Study  and  Practice 
of  Alchymy  (67). 

Get  what  you  can,  and  what  you  get  hold; 
'Tis  the  Stone  that  will  turn  all  your  lead  into  gold 
(68). 

.  .  .  Surely  to  alchemy  this  right  is  due,  that  it  may 
be  compared  to  the  husbandman  whereof  Aesop 
makes  the  fable;  that,  when  he  died,  told  his  sons 
that  he  had  left  unto  them  gold  buried  underground 
in  his  vineyard;  and  they  digged  over  all  the  ground, 
and  gold  they  found  none;  but  by  reason  of  their 
stirring  and  digging  the  mould  about  the  roots  of 
their  vines,  they  had  a  great  vintage  the  year  follow 
ing:  so  assuredly  the  search  and  stir  to  make  gold 
hath  brought  to  light  a  great  number  of  good  and 
fruitful  inventions  and  experiments  .  .  .  (1). 

Chemistry  began  by  saying  it  would  change  the  baser 
metals  into  gold.  By  not  doing  that  it  has  done  much 
greater  things  (64). 


3 


Elements  of  the  alchemists 


The  alchemists  never  succeeded  in  making  gold  from  base  metals, 
yet  their  experiments,  recorded  under  a  mystical  and  intentionally 
obscure  terminology,  gradually  revealed  metallic  arsenic  and 
antimony.  Bismuth  was  discovered  by  practical  miners.  Finally, 
in  the  latter  part  of  the  seventeenth  century,  the  pale  light  of 
phosphorus  began  to  illumine  the  dark  secrets  of  alchemy  and  to 
disclose  the  steady  advance  of  scientific  chemistry. 


he  part  played  in  ancient  civilizations  by  gold,  silver,  copper, 
iron,  lead,  tin,  mercury,  carbon,  and  sulfur  has  already  been  shown. 
Certain  other  elements,  although  their  lineage  is  not  quite  so  ancient, 
have  nevertheless  had  a  history  that  extends  far  back  through  the  cen 
turies.  In  this  group  may  be  mentioned  arsenic,  antimony,  bismuth,  and 
phosphorus;  and,  strangely  enough,  these  four  simple  substances  have 
so  many  characteristics  in  common  that  they  constitute  one  of  the  groups 
in  the  system  of  classification  now  universally  used  by  chemists.  Their 
early  history  is  so  shrouded  in  uncertainty  that  only  in  the  case  of 
phosphorus  is  it  possible  to  assign  the  honor  of  discovery  difmitely  to 
any  person.  They  were  brought  to  light  however  during  the  long  vision 
ary  search  by  alchemists  for  the  philosophers'  stone  that  would  convert 
base  metals  into  gold  and  by  iatrochemists  for  the  elixir  of  life  that  would 
prolong  life  indefinitely  and  through  the  efforts  of  miners.  Reflecting 
on  the  folly  of  attempts  to  prepare  gold  from  sulfur  and  mercury,  Leo 
nardo  da  Vinci  wrote  in  one  of  his  notebooks,  "If,  however,  insensate 
avarice  should  drive  you  into  such  error,  why  do  you  not  go  to  the 
mines  where  nature  produces  this  gold,  and  there  become  her  disciple? 
She  will  completely  cure  you  of  your  folly  by  showing  you  that  nothing 
which  you  employ  in  your  furnace  will  be  numbered  among  the  things 
which  she  employs  in  order  to  produce  this  gold.  For  there  is  there  no 
quicksilver,  no  sulphur  of  any  kind,  no  fire  nor  other  heat  than  that  of 
nature  giving  life  to  our  world;  and  she  will  show  you  the  veins  of  the 
gold  spreading  through  the  stone  .  .  ."  (69). 

91 


92  DISCOVERY  OF  THE  ELEMENTS 

ARSENIC 

"For  smelter  fumes  have  I  been  named. 

I  am  an  evil,  poisonous  smoke  .   .   . 
But  when  from  poison  I  am  freed, 

Through  art  and  sleight  of  hand, 
Then  can  I  cure  both  man  and  beast, 

From  dire  disease  ofttimes  direct  them; 
But  prepare  me  correctly,  and  take  great  care 

That  you  faithfully  keep  watchful  guard  over  me; 
For  else  am  I  poison,  and  poison  remain, 

That  pierces  the  heart  of  many  a  one."  (36)* 

The  so-called  "arsenic"  of  the  Greeks  and  Romans  consisted  of  the 
poisonous  sulfides,  orpiment  and  sandarac?  mined  with  heavy  loss  of  life 
by  slave  labor  (2).  Both  Pliny  the  Elder  and  Dioscorides  were  familiar 
with  orpiment  and  realgar  (sandarac)  (70).  The  latter  mentioned  that 
"Arsenicum"  and  "Sandaracha"  occur  in  the  same  mines,  that  sandarac 
has  a  "brimstone-like"  odor,  and  that  these  two  ores  are  roasted  in  the 
same  manner  (71). 

No  one  knows  who  first  isolated  the  metal,  but  this  honor  is  some 
times  accredited  to  Albert  the  Great  ( Albertus  Magnus,  1193-1280),  who 
obtained  it  by  heating  orpiment  with  soap  (3).  Paracelsus  (15),  the 
eccentric  and  boastful  medical  alchemist  of  the  sixteenth  century,  men 
tioned  a  process  for  obtaining  metallic  arsenic,  "white  like  silver,"  by 
heating  the  so-called  "arsenic"  of  the  ancients  with  egg  shells  (18,  66). 
Berthelot  believed,  however,  that  metallic  arsenic  was  known  much 
earlier  than  this,  for  it  is  easily  reduced  from  its  ores.  Since  it  sublimes 
easily,  and  readily  forms  soft  alloys  with  other  metals,  and  since  the 
arsenic  sulfide,  realgar,  looks  very  much  like  the  corresponding  mercury 
ore,  cinnabar,  the  alchemists  regarded  arsenic  as  a  kind  of  quicksilver. 
The  Pseudo-Democritus  gave  the  following  method  of  reducing  the  ore: 
"Fix  the  mercury  obtained  from  arsenic  (sulfide)  or  from  sandarac,  throw 
it  on  to  copper  and  iron  treated  with  sulfur,  and  the  metal  will  become 
white"  (3,17,23). 

Signor  Marcello  Muccioli  published  in  Archeion  an  article  on  the 
knowledge  of  arsenic  possessed  by  the  Chinese  in  about  1600,  as  ex 
hibited  in  the  Pen  Ts'ao  Kan-Mu  (or  Kang-mu),  a  52- volume  encyclo 
pedia  on  materia  medica  (37).  Yoshio  Mikami  states  that  this  work 

*  "Mein  Nahme  heisset  Hutten-Rauchf  Und  bin  ein  gifftiger  boser  Schmauch  / 

Da  aber  Ich  verlier  den  Gift/  Durch  Kunst  und  rechte  Handgrifff  So  kan  Ich 
Menschen  und  Vieh  curirenf  Auss  boser  Kranckheit  offtmals  fiihren/  Doch  bereit  mit 
rechtf  und  hab  gut  Acht/  Dass  du  halst  mit  mir  gute  Wachtf  Sonst  bin  Ich  Gift  und 
bleibe  Gift/  Das  manchems  Hertz  im  Leib  absticM'  (36). 


ELEMENTS  OF  THE  ALCHEMISTS 


93 


Albertus  Magnus,  1193- 
1280.  German  Domini 
can  scholar  and  alchem 
ist  who  interpreted  Aris 
totle  to  the  Latin  races. 
Author  of  "De  Minerali- 
bus."  He  also  contrib 
uted  to  mechanics,  geog 
raphy,  and  biology.  See 
also  ref.  ,(63). 


was  printed  in  1590  and  that  it  was  the  result  o£  thirty  years  of  scholarly 
labor  by  its  author,  Li  Shih-chen  (38).  The  Chinese  were  thoroughly 
familiar  with  the  poisonous  properties  of  arsenic,  and  knew  how  to  test 
whether  or  not  a  person  had  been  poisoned  by  it.  They  used  it  to  kill 
mice  in  their  fields  and  insects  in  their  rice  plantations.  Chinese  persons 
were  sometimes  poisoned  by  drinking  beverages  which  had  stood  for  some 
time  in  new  tin  vessels.  The  author  of  the  Pen  Ts'ao  attributed  these 


94  DISCOVERY  OF  THE  ELEMENTS 

cases  to  improper  purification  of  tin  prepared  from  minerals  containing 
arsenic  (37).  After  making  erasures  in  their  manuscripts  (which  were 
written  on  yellow  paper),  ancient  Chinese  scholars  covered  them  neatly 
with  a  yellow  varnish  containing  finely  pulverized  orpiment.  Most  of 
the  orpiment  was  used  by  artists,  however,  as  a  pigment  (37). 


Rudolf  Winderlich,  1876-1951.  Ad 
vanced-studies  adviser  at  the  sec 
ondary  school  at  Oldenburg  in  Olden 
burg.  Author  of  excellent  textbooks 
containing  valuable  notes  on  the  his 
tory  of  chemistry;  of  the  books 
"Chemie  und  Kultur,"  "Chemie  fur 
Jedermann,"  and  "Das  Ding";  and  of 
many  articles  in  educational  journals. 
Contributor  to  "Das  Buch  der  grossen 
Chemiker."  See  ref.  (61). 


In  1649  Johann  Schroeder  published  a  pharmacopoeia  in  which  he 
gave  two  methods  of  obtaining  metallic  arsenic:  (1)  by  decomposing 
orpiment,  arsenious  sulfide,  with  lime  and  (2)  by  reducing  arsenious 
oxide  with  charcoal. 

E.-F.  Geoff roy  (1672-1731)  recognized  three  kinds  of  arsenic: 
orpiment,  realgar,  and  "arsenic  properly  so  called,"  which  was  extracted 
from  the  cobalt  ores  of  Saxony  and  Bohemia.  "German  Cobalt  of  the 
Shops,  Cadmia  Metallica  of  Agricola,"  said  he,  "is  a  ponderous,  hard, 
fossil  Substance,  almost  black,  not  unlike  Antimony  or  some  Kinds  of 
Pyrites,  emitting  a  strong  sulphureous  Smell  when  burnt,  often  mixed 
with  Copper,  sometimes  with  Silver.  It  is  dug  out  of  Mines  in  Saxony, 
near  Goslar;  in  Bohemia,  in  the  Valley  of  Joachim  [Joachimsthal];  and 
in  England  in  the  Mendip  Hills,  in  great  Quantities.  It  has  so  strong 
a  Corrosive  Quality  as  sometimes  to  burn  and  ulcerate  the  Hands  and  Feet 
of  the  Miners,  and  it  is  a  deadly  Poison  for  all  known  Animals.  All  the 
three  Kinds  of  Arsenick  are  extracted  from  it,  and  it  likewise  serves  to 
make  Zaffera,  used  by  Potters  in  giving  a  blue  Colour  to  their  Vessels: 


ELEMENTS  OF  THE  ALCHEMISTS  95 

and  the  Encaustum  C&ruleum,  or  that  Kind  of  Blue  sometimes  used 
by  Painters,  and  often  by  Women  to  mix  with  Starch  for  whitening  and 
stiffening  Linen"  (72).  The  blue  color  was  undoubtedly  imparted  by 
the  cobalt  in  the  ore. 

The  metallic  nature  of  arsenic  was  thoroughly  established  through 
the  researches  of  J.  F.  Henckel  (or  Henkel),  who  in  1725  told  how  to 
prepare  it  by  sublimation,  and  of  Georg  Brandt,  who  investigated  its 
properties  in  1733,  noticed  its  amphoteric  nature,  and  was  surprised  that 
"the  same  substance  should  dissolve  in  so  many  different  menstrua"  (16, 
21,  76).  Bishop  Johan  Browall  (1744),  A.-M.  Monnet  (1774),  and  J.  H. 
Pott  (1720)  also  studied  it  (3,  22). 

As  early  as  1738  C.-J.  Geoffroy  (Geoffroy  the  Younger)  noticed  that 
when  most  kinds  of  tin  were  heated  they  gave  off  fumes  which  seemed 
to  contain  arsenic.  J.  F.  Henckel,  in  his  translation  of  de  Respour's 
"Mineral-Geist,"  described  a  test  for  arsenic  in  tin.  In  1747  A.  S.  Marg- 
graf  reported  the  presence  of  arsenic  in  all  the  specimens  of  tin  which 
he  examined  (73,  74). 

ANTIMONY 

"But  antimony,  like  mercury,  can  best  be  compared  to  a  round  circle  with 
out  end,  .  .  .  and  the  more  one  investigates  it,  by  suitable  means,  the  more  one 
discovers  in  it  and  learns  from  it;  it  cannot  be  mastered,  in  short,  by  one  person 
alone  because  of  the  shortness  of  human  life."  (58) 

Antimony,  like  arsenic,  was  known  to  the  ancients,  but  perhaps  only 
in  the  form  of  its  sulfide,  which  Oriental  women  of  leisure  used  to  use  to 
darken  and  beautify  their  eyebrows  (4). 


0=0 


From  Peters's  "Aus  pharmazeutischer  Vorzeit 
in  Bild  und  Wort" 


Seventeenth-century   alchemistic   symbol.      Ar 
senic   (left)    and  antimony   (above).     For  the 
history  of  chemical  symbols  see  ref.   ( 61 ) . 


96  DISCOVERY  OF  THE  ELEMENTS 

In  the  revised  Douai  Bible,  the  account  of  Jezebel's  ( JezabeFs)  death 
begins  as  follows:  "And  Jehu  came  into  Jezrahel:  But  Jezabel  hearing  of 
his  coming  in,  painted  her  face  with  stibic  stone  .  .  ."  (IV  Kings  9,  30). 
The  modern  Spanish  translation  states  that  Jezebel  "se  pinto  los  ojos  con 
antimonio"  (SI).  The  authorized  English  Version  does  not  mention 
the  nature  of  the  cosmetic  (II  Kings  9,  30).  The  harmful  custom  of 
painting  the  eyes  was  condemned  by  Jeremiah  and  by  Ezekiel  (Ezek.  23, 
40).  Jeremias  4,  30  of  the  revised  Douai  Bible  reads  as  follows:  "But 
when  thou  art  spoiled,  what  wilt  thou  do?  Though  thou  clothest  thyself 
with  scarlet,  though  thou  deckest  thee  with  ornaments  of  gold,  and  paint- 
est  thy  eyes  with  stibick-stone,  thou  shalt  dress  thyself  out  in  vain:  thy 
lovers  have  despised  thee,  they  will  seek  thy  life."  The  modern  Spanish 
translation  reads:  "aunque  te  pintes  los  ojos  con  antimonio"  (81).  Here, 
too,  the  Authorized  English  Version  does  not  mention  the  cosmetic,  but 
merely  reads:  "though  thou  rentest  thy  face  with  painting"  (Jer.  4,  30). 

The"stibick-stone"  was  undoubtedly  stibnite,  or  antimonious  sulfide. 
Oriental  women  used  the  black,  pulverized  mineral  as  an  eye  paint  for 
increasing  the  apparent  size  of  the  eyes,  giving  them  the  staring  pro 
truding  appearance  characteristic  of  Egyptian  portraits.  Job's  youngest 
daughter  was  named  Kerenhappuch,  which  means  "horn  of  eye-paint" 
(82).  "And  in  all  the  land  were  no  women  found  so  fair"  (Job  42,  14- 
15).  Although  T.  K.  Cheyne  questions  this  interpretation  of  the  name, 
the  Challoner  revision  of  the  Douai-Reims  Bible  gives  the  Latin  names  of 
Job's  daughters  as  follows:  "And  he  called  the  name  of  one  Dies,  and 
the  name  of  the  second  Cassia,  and  the  name  of  the  third  Cornustibif 
(horn  of  antimony)  (83,  84). 

Ancient  eye  paints  often  contained  cupric  oxide,  lead  sulfide,  and 
lampblack.  Their  most  costly  constituent,  however,  was  the  stibnite, 
which  had  to  be  imported  from  distant  countries  (85).  The  Hebrew 
word  for  this  eye  paint  was  puk  (85). 

Geoffroy  the  Elder  mentioned  that  "Among  the  Ancients,  Antimony 
[stibnite]  was  used  to  dye  the  Supercilia  and  Cilia  Black.  Accordingly 
we  find  in  Scripture  that  the  wicked  Queen  Jezabel  [sic],  in  order  to 
charm  the  King  her  Husband,  painted  her  Eyes  with  Antimony;  and 
the  Women  who  used  that  Practice  are  also  reproved  by  the  Prophets" 
(75). 

A.  Lucas  stated  that  antimony  and  its  compounds  were  rarely  used  in 
ancient  Egypt.  He  mentioned  one  example  of  a  Nineteenth-Dynasty 
eye  paint  consisting  of  antimony  sulfide;  the  use  in  the  same  Dynasty  of 
antimony  and  lead  to  color  glass  yellow;  some  small  beads  of  metallic 
antimony,  probably  made  from  native  metal  in  the  Twenty-second  Dy 
nasty  (945-745  B.C.);  a  tablet  of  metallic  antimony  which  M.  Julius 


ELEMENTS  OF  THE  ALCHEMISTS 


97 


Oppert  found  at  Khorsabad;  and  a  vase  of  pure  antimony  which  M. 
Sarzec  found  at  Tello  and  which  M.  Berthelot  described  in  the  Comptes 
rendus  in  1887  (77).  Stibnite,  or  Stimmi,  is  mentioned  twice  in  the  Ebers 
medical  papyrus  of  the  sixteenth  century  B.C.  (78). 

Berthelot' s  belief  that  metallic  antimony  was  known  to  the  ancient 
Chaldeans  was  based  on  his  analysis  of  the  most  unusual  vase  that  had 


From  N.  LeFeure's  "Cours  de  Chymie"  1751 

Calcination  of  Antimony.    0,  the  table;  &,  the  mirror,  which,  can  be  raised 

or  lowered;   c,  the  stone  or  the  slab,   on  which  is  placed  the  powdered 

antimony;   d,  the  adept  adjusting  the  mirror  and  moving  the   antimony; 

e,  the  light  focused  by  the  mirror. 


been  brought  to  the  Louvre  from  the  rains  of  Tello,  and  which  he  found  to 
consist  of  pure  metallic  antimony  containing  only  a  trace  of  iron  (5,  19). 
He  also  quoted  the  following  passage  from  Dioscorides:  "One  roasts  this 
ore  ( antimonious  sulfide )  by  placing  it  on  charcoal  and  heating  to  incan 
descence;  if  one  continues  the  roasting,  it  changes  into  lead"  (5).  Pliny 
issued  the  same  warning  in  his  description  of  the  preparation  of  antimony 


98 


DISCOVERY  OF  THE  ELEMENTS 


medicinals,  when  he  said:  "But  the  main  thing  of  all  is  to  observe  such  a 
degree  of  nicety  in  heating  it,  as  not  to  let  it  become  lead"  (4).  Hence  it 
is  possible  that  the  Greeks  and  Romans,  like  the  Chaldeans,  knew  how  to 
obtain  antimony,  but  since  they  did  not  have  adequate  methods  of  dis 
tinguishing  between  metals,  they  applied  the  indefinite  term  "lead"  to  all 
those  that  were  soft,  easily  fusible,  and  black. 

Georgius  Agricola,  in  the  sixteenth  century  A.D.,  was  familiar  with 
metallic  antimony  and  an  important  use  of  it.  "Stibium,"  said  he  in  his 
;<De  natura  fossilium,"  "when  smelted  in  the  crucible  and  refined,  has  as 


Basilius  Valentinus.  Although  the 
collection  of  chemical  writings  at 
tributed  to  the  fifteenth-century 
Benedictine  monk,  Basilius  Valen 
tinus,  contains  this  alleged  por 
trait,  there  is  no  conclusive  evi 
dence  that  such  a  person  ever 
lived.  Although  the  "Triumphal 
Chariot  of  Antimony"  and  other 
writings  commonly  attributed  to 
him  are  much  too  modern  for  the 
fifteenth  century,  they  are  never 
theless  of  great  historical  value. 


much  right  to  be  regarded  as  a  proper  metal  as  is  accorded  to  lead  by 
writers.  If,  when  smelted,  a  certain  portion  be  added  to  tin,  a  bookseller's 
alloy  is  produced  from  which  the  type  is  made  that  is  used  by  those  who 
print  books  on  paper"  ( 39 ) . 

Since  the  alchemists  considered  natural  antimony  minerals  to  be 
the  most  suitable  raw  material  for  the  transmutation  of  metals  into  gold, 
alchemical  literature  abounds  in  references  to  antimony  (65).  The  most 
famous  of  the  early  monographs  on  this  element  is  the  "Triumphal  Chariot 
of  Antimony,"  which  first  appeared  in  1604,  in  German.  Johann  Tholde, 
operator  of  a  saltworks  in  Frankenhausen,  Thuringia,  the  editor  of  this 
work,  claimed  that  it  had  been  written  by  a  fifteenth-century  Benedictine 
monk,  Basilius  Valentinus  (3,  6).  Since  no  conclusive  evidence  of  the 
existence  of  this  monk  has  been  unearthed,  and  since  the  literary  style 


ELEMENTS  OF  THE  ALCHEMISTS 


99 


of  the  "Triumphal  Chariot"  is  much  too  modern  for  a  fifteenth-century 
manuscript,  many  historians  of  chemistry  have  concluded  that  it  must 
have  been  written  in  the  latter  part  of  the  sixteenth  century,  possibly  by 
Tholde  himself.  Felix  Fritz,  however,  has  concluded  from  comparison 
with  the  "Haligraphia"  and  other  authentic  publications  of  J.  Tholde  that 
he  cannot  have  been  the  author  of  the  "Triumphal  Chariot"  nor  of  the 
other  writings  attributed  to  Basilius  (40). 

In  1707  Nicolas  Lemery  published  his  famous  "Treatise  on  Anti 
mony."  He  was  born  at  Rouen  on  November  17,  1645.  After  studying 
pharmacy  there  under  one  of  his  relatives,  he  went  to  Paris  in  1666  to 
complete  his  education.  Dissatisfied  with  his  progress  under  the  unso 
ciable  but  scholarly  Christophe  Glaser,  demonstrator  of  chemistry  at  the 
Jardin  du  Roi,  he  resolved  to  tour  France  and  learn  firsthand  from  the 
greatest  chemists  of  his  day  (43).  Dr.  Clara  DeMilt  believed  however 
that  Lemery  gained  many  of  the  ideas  presented  in  his  textbook  from 


Nicolas     Lemery,     M.D.,     1645-1715. 

French  chemist.     Author  of  "Cours  de 

Chymie,"    one    of    the    textbooks    that 

Scheele   studied,   and  of  a  treatise  on 

antimony. 


Glaser  (43).  Returning  to  Paris  in  1672,  Lemery  lectured  to  groups  of 
students  who  rebelled  against  the  prevailing  ignorance  and  prejudice  of 
the  iatrochemists  (41). 

When  M.  Lemery  had  to  choose  between  the  two  degrees,  Doctor 
of  Medicine  or  Master  Apothecary,  he  selected  the  latter  first  because  of 
its  closer  relation  to  chemistry.  B.-B.  de  Fontenelle  described  his  public 
laboratory  in  the  Rue  Galande  as  'less  a  room  than  a  cellar,  and  almost 


100  DISCOVERY  OF  THE  ELEMENTS 

a  magic  cavern,  illumined  only  by  the  light  of  the  furnaces;  yet  the  influx 
of  people  was  so  great  that  there  was  scarcely  enough  room  for  his  opera 
tions.  Even  women,  carried  along  by  fashion,  had  the  audacity  to  show 
themselves  at  such  learned  assemblies"  (41). 

Students  came  from  all  parts  of  Europe  to  live  at  his  boarding 
school,  "and  the  rooms  of  the  quarter  were  filled  with  half-pensioners, 
who  wished  at  least  to  eat  at  his  home."  His  pharmaceutical  preparations 
had  a  large  sale,  and  the  profits  from  his  "bismuth  magistery,"  a  cosmetic, 
were  sufficient  for  all  the  expenses  of  his  household.  In  1675  he  published 
his  famous  "Cours  de  Chymie,"  which,  unlike  most  scientific  books,  sold 
out  edition  after  edition  "like  a  work  of  romance  or  satire." 

When  Lemery  was  received  into  the  Academy  of  Sciences  in  1699, 
he  decided  to  make  a  thorough  analysis  of  the  mineral  known  as  antimony 
[stibnite]  in  a  search  for  useful  medicaments.  After  reading  his  paper 
in  instalments  to  the  Academy,  he  finally  published  it  in  1707  as  the 
"Treatise  on  Antimony."  "When  I  resolved  to  study  antimony  thoroughly 
in  all  its  aspects,"  said  he,  "I  believed  it  proper  to  begin  with  some 
reflections  on  the  nature  of  this  compound  and  the  places  where  it  occurs; 
on  the  names  which  were  applied  to  it,  and  their  diversity;  on  how 
to  select  it;  and  on  its  medicinal  virtues  (41 ). 

"Antimony,"  said  Lemery,  "is  a  heavy,  fragile,  black,  shining,  odor 
less,  insipid,  and  very  sulfurous  mineral  crystallizing  in  laminae  or  in  long 
needles.  It  occurs  near  the  metals  in  many  European  mines,  in  Hungary, 
in  Transylvania,  in  Brittany,  in  Poitou,  and  in  Avernia.  In  Latin  it  is 
called  antimonium  or  stibium.  The  alchemists,  who  abound  in  high- 
sounding  names,  have  called  it  the  red  lion  or  wolf,  because  in  the  fire 
it  devours  the  greater  part  of  the  metals;  believing  that  many  metals  were 
derived  from  it,  they  have  called  it  the  root  of  the  metals;  because  it 
receives  various  forms  and  colors,  they  have  sometimes  called  it  Proteus; 
sometimes  sacred  lead,  or  philosophers'  lead,  because  they  believed  that, 
since  this  mineral  devours  many  metals,  it  must  be  related  to  lead,  which 
combines  with  many  metallic  substances  (41). 

"Among  the  merchants,"  continued  Lemery,  "we  find  two  general 
species  of  antimony,  the  unworked  mineral  and  the  artificial:  the  former 
is  taken  from  the  mine  loaded  or  mixed  with  many  rock  fragments,  which 
the  artisans  call  gangue.  .  .  .  This  kind  of  antimony  is  not  very  common 
at  the  apothecaries'  shops  because  it  does  not  sell  well.  .  .  . 

"The  other  kind  of  antimony,"  said  Lemery,  "is  that  commonly  found 
at  the  apothecaries';  it  is  not  different  from  the  first  except  that  it  has 
been  purified  from  its  stony  and  earthy  constituents.  To  purify  it,  the 
antimony  taken  from  the  mine  is  melted  in  vessels  or  crucibles  in  the  fire, 
then-  removed  by  means  of  a  perforated  iron  ladle  to  other  vessels;  the 


ELEMENTS  OF  THE  ALCHEMISTS  101 


IOHANNIS..  ' 

SCHRODER! 


MFD  1C  I  GfcRMANl 

ss. 

PHARMACOPOEIA 
Clivmto1** 


From  LaWall's  "Four  Thousand  Years  of  Pharmacy" 
Frontispiece  from  Johann  Schroeder's  Pharmacopeia,  1646 


102  DISCOVERY  OF  THE  ELEMENTS 

dirt  which  remains  on  the  strainer  is  thrown  away,  and  when  the  antimony 
has  become  cold,  the  vessels  are  broken  open  and  removed,  and  it  [the 
antimony]  is  sent  to  us  in  loaves  as  we  see  it.  The  antimony  from  Poitou 
is  the  handsomest  and  best,  because  most  carefully  purified.  .  "  (41). 
Before  the  discovery  of  stibnite  in  France,  small  specimens  of  it  had  been 
imported  from  Hungary. 

By  heating  a  mixture  of  crude,  pulverized  stibnite,  saltpeter,  and 
"red  tartar"  to  redness  in  a  crucible,  Lemery  obtained  the  metal,  which 
fused  completely,  and  condensed  on  cooling  to  form  a  massive,  shining 
solid  with  the  characteristic  stellar  structure  of  antimony  on  its  surface 
(41).  This  highly  specialized  investigation  led  Fontenelle  to  foresee  the 
great  chemical  monographs  of  today.  "One  might  learn  from  this 
example,"  said  he,  "that  the  study  of  a  single  mixture  is  almost  limitless 
and  that  each  in  particular  might  have  its  own  chemist"  (41). 

Du  Monstier,  the  editor  of  Nicolas  Le  Fevre's  "Cours  de  Chymie," 
was  more  critical  of  Lemer/s  work.  "A  treatise  that  he  published  on 
antimony;'  said  Du  Monstier,  "found  itself  exposed  to  the  criticism  of 
persons  better  informed  than  he  on  this  mineral.  I  have  been  not  a  little 
surprised  to  see  with  what  boldness  he  gives  to  sick  persons  antimony 
preparations  which  he  devises  and  risks  for  the  first  time.  One  feels 
nevertheless  on  reading  it  that  he  has  never  seen  those  of  Basil  Valentine 
and  of  Suchten,  both  Germans  whose  works  are  held  in  high  esteem  by 
connoisseurs"  (42). 

Paul-Antoine  Cap's  biographical  sketch  of  Lemery,  written  with 
the  literary  elegance  of  a  French  classic,  opens  with  an  imaginary  word 
picture  of  Lemery  entertaining  in  his  laboratory  his  cosmopolitan  friend 
Wilhelm  Homberg.  "At  the  end  of  the  room,  opposite  the  door,"  said 
Cap,  "one  noticed  an  immense  furnace  of  solid  and  massive  construction, 
surmounted  by  a  basket  full  of  instruments  and  various  kinds  of  apparatus. 
Retorts  and  flasks  there  contended  for  space  with  matrasses,  siphons,  and 
aludels  [earthen  subliming  pots].  Around  this  monumental  furnace  were 
placed  other  portable  furnaces  and  polychrests,  with  their  alembics,  refrig 
erants,  serpentines,  rosaries,  athanors,  sand  baths,  and  reverberatory  fur 
naces,  with  their  domes,  their  moor's  head  stills,  and  their  copper  or  tin 
copings.  In  the  center  of  this  great  room  one  saw  a  large  table  covered 
with  utensils,  urns,  scorifiers,  two-stage  and  three-stage  glass  alembics, 
and  subliming  apparatus  with  long  cones  arranged  in  pyramids.  A  copper 
lamp  suspended  from  the  ceiling  swayed  in  the  air,  chemical  symbols, 
arithmetical  tables,  slates  streaked  with  chalk  covered  the  walls  of  the 
room,  and  at  each  corner,  hourglasses  of  various  sizes  served  for  measuring 
time  and  regulating  the  duration  of  experiments. 

"This  laboratory,"  said  Cap,  "one  could  judge  at  a  glance,  was  not 


ELEMENTS  OF  THE  ALCHEMISTS  103 

that  of  a  sixteenth-century  alchemist.  One  did  not  recognize  here,  by 
the  peculiarity  of  their  forms,  the  bizarre  ideas  conceived  by  these  men 
on  the  nature  of  elements  and  mixtures.  One  saw  none  of  those  emblems, 
allegories,  and  symbolic  figures  with  the  aid  of  which  they  thought  to 
hide  from  the  knowledge  of  the  common  man  their  pretended  secrets, 
already  so  obscure  even  for  the  true  adepts.  Nothing  there  suggested 
mystery,  charlatanism,  or  occultism;  on  the  contrary,  everything  bore  the 
stamp  of  laborious  study,  of  useful  science;  everything  bespoke  the  modest 
scholar  who  devoted  his  life,  in  good  faith  and  unreservedly,  to  the  search 
for  truth"  (44). 

After  the  publication  of  his  monograph  on  antimony,  Lemery  began 
to  suffer  from  paralytic  strokes  and  apoplexy,  which  on  June  19,  1715, 
brought  his  life  to  a  close.  According  to  B.  Le  Bovier  de  Fontenelle,  "most 
of  Europe  learned  chemistry  from  him,  and  most  of  the  great  chemists, 
French  or  foreign,  have  rendered  homage  to  him  by  their  learning.  He 
was  a  man  of  unceasing  industry,  knowing  only  the  bedside  of  his  patients, 
his  study,  his  laboratory,  and  the  Academy,  and  showing  that  he  who 
wastes  no  time  has  plenty  of  it"  ( 41 ) . 

Early  Uses  of  Antimony.  Geoffrey  the  Elder  mentioned  the  use  of 
cups  of  metallic  antimony  "which  communicate  an  emetick  Quality  to 
Wine  which  has  stood  in  them  for  a  Night's  time"  (75).  "Besides  the 
Medical  Uses  of  Antimony,"  said  he,  "it  is  employed  by  several  Artificers, 
to  give  Silver  Sound  to  Tin,  in  casting  Bells,  making  Metalline  Specula, 
and  Types  for  Printing,  etc.  It  is  likewise  used  by  Goldsmiths  in  refining 
Gold,  for  when  melted  with  that  Metal,  it  destroys  all  other  Metals  that 
can  be  mixed  with  it,  Silver  itself  not  excepted,  and  turns  them  to  Dross" 
(75). 

Native  Antimony.  In  1748  Anton  von  Svab  found  that  the  so-called 
"arsenical  pyrite"  from  the  Sala  mine  in  Sweden  was  native  antimony 
(76,  79).  In  a  review  in  1781  of  Torbern  Bergman's  dissertation  on  the 
wet  assay  of  minerals,  one  finds  the  statement  that  "the  native  antimony 
(Spiessglaskonig)  discovered  by  von  Svab  is  also  found,  although  but 
rarely,  outside  Sweden  in  a  quartzose  matrix"  (80). 

BISMUTH 

The  Germanisches  Museum  in  Nuremberg  preserved  a  collection 
of  boxes,  caskets,  chests,  and  little  cupboards  decorated  in  bright  colors 
painted  over  a  background  of  metallic  bismuth  (28,  45).  In  his  "History 
of  Bismuth  from  1400  to  1800,"  E.  O.  von  Lippmann  stated  that  one  of 
these  was  made  in  about  1480  ( 46 ) .  By  1572  this  art  had  developed  into 
a  craft  there,  and  in  1613  its  artisans  were  incorporated  into  a  guild  (47). 


104 


DISCOVERY  OF  THE  ELEMENTS 


Edmund  Oskar  von  Lippmann,  1857-1940.  Austrian-German  historian 
of  chemistry  and  sugar  chemist  and  technologist.  Author  of  authoritative 
books  on  the  chemistry  and  history  of  sugar,  history  of  the  magnetic 
needle,  and  history  of  alchemy  and  chemistry.  Head  of  the  large  sugar 
refinery  at  Halle.  Honorary  professor  of  the  history  of  chemistry  at  the 
University  of  Halle.  See  also  ref.  (87). 


ELEMENTS  OF  THE  ALCHEMISTS  105 

F.  Wibel  described  a  wooden  casket  in  the  Museum  of  Useful  Arts  at  Ham 
burg,  made  in  1557.  Over  a  chalk  background  attached  with  wax  or 
glue,  it  has  a  metallic  surface  about  one  millimeter  thick,  overlaid  with 
gold  or  amber  lacquer.  Investigation  of  this  surface  proved  it  to  be 
bismuth.  In  the  latter  part  of  the  eighteenth  century,  bismuth  painting 
was  superseded  by  a  cheaper  process  in  which  perfected  lacquers  were 
applied  directly  to  the  wood  (47). 

In  the  middle  of  the  fifteenth  century  the  demand  for  bismuth 
increased.  The  early  Gutenberg  printing  presses  first  used  type  cut  from 
brass,  and  later,  type  cast  from  metals,  such  as  lead,  copper,  or  tin.  In 
about  1450  a  secret  method  of  casting  type  from  a  bismuth  alloy  came 
into  use  (46).  According  to  E.  O.  von  Lippmann,  the  earliest  mining 
publication  to  mention  bismuth  is  that  of  Riilein  von  Kalbe,  Burgomaster 
of  Freiberg,  who  in  1505  referred  to  "Wysmudertz"  as  something  already 
well  known. 

In  his  "Heaven  of  the  Philosophers/'  Paracelsus  (1493-1541)  made 
a  vague  allusion  to  bismuth:  £Two  kinds  of  Antimony  are  found:  one 
the  common  black,  by  which  Sol  [gold]  is  purified  when  liquefied  therein. 
This  has  the  closest  affinity  with  Saturn  [lead].  The  other  kind  is  the 
white,  which  is  also  called  Magnesia  and  Bismuth.  It  has  great  affinity 
with  Jupiter  [tin],  and  when  mixed  with  the  other  Antimony  it  augments 
Luna  [silver]"  (48). 

Georgius  Agricola,  a  contemporary  of  Paracelsus,  described  the 
properties  of  bismuth  in  much  greater  detail  and  told  how  it  was  extracted 
from  ores  mined  near  Schneeberg  in  the  Saxon-Bohemian  Erzgebirge. 
In  his  book  "Bermannus,"  Bermannus  says  to  Nsevius,  "this  which  just 
now  I  said  we  called  bisemutum  cannot  correctly  be  called  plumbum  can- 
didum  (tin)  nor  nigrum  (lead),  but  is  different  from  both  and  is  a  third 
one"  (49).  In  believing  it  to  be  a  specific  metal,  different  from  all  others, 
Agricola  was  far  in  advance  of  his  age,  for  the  idea  that  bismuth  was  a 
kind  of  lead  persisted  even  into  the  eighteenth  century  (7).  The  miners 
believed  that  there  were  three  kinds  of  lead  ( ordinary  lead,  tin,  and  bis 
muth)  and  that  bismuth  had  progressed  farthest  in  its  transmutation 
into  silver.  When  they  struck  a  vein  of  bismuth  they  said  naively  and 
sadly,  "Alas,  we  have  corne  too  soon"  (7).  Since  they  usually  found 
silver  below  the  bismuth,  they  called  the  latter  "tectum  argentf  or  "roof 
of  silver"  (24). 

In  his  "De  re  metallica '  Agricola  gave  several  methods  of  obtaining 
the  metal  by  simple  liquation  of  the  native  bismuth  or  by  reduction  with 
charcoal.  Pulverized  charcoal  was  placed  in  a  small,  dry  pit,  and  a  fire  of 
beech  wood  was  kindled  over  it.  When  the  ore  was  thrown  into  the  fire, 
the  molten  bismuth  dripped  out  of  it  into  the  pit.  The  solidified  cakes 
were  later  purified  in  a  crucible  (24). 


106  DISCOVERY  OF  THE  ELEMENTS 

After  discussing  the  prevalent  belief  that  the  growth  of  precious 
stones  and  metals  was  governed  by  the  stars,  Padre  Alvaro  Alonso  Barba 
stated  in  1640  in  his  "Arte  de  los  Metales":  "But  this  subordination  and 
application  is  uncertain,  as  is  also  the  conceit  that  Mettals  are  but  seven 
in  number,  whereas  it  is  very  probable  that  in  the  bowels  of  the  Earth 
there  be  more  sorts  than  we  yet  know  A  few  years  ago  in  the  mountains 
of  Sudnos  in  Bohemia  was  found  a  Mettal  between  Tin  and  Lead,  and  yet 
distinct  from  them  both:  theie  are  but  few  that  know  of  it,  and  'tis 
very  possible  more  Mettals  also  may  have  escaped  the  notice  of  the 
generality.  And  if  one  should  admit  the  subordination  and  resemblance 
between  Mettals  and  the  Planets,  modern  experience,  by  excellent  Telis- 
copes  has  discovered  that  they  are  more  than  seven.  Gallileo  de  Galiles 
[sic!]  has  written  a  Treatise  of  the  Satelites  of  Jupiter,  where  one  may 
find  curious  observations  of  the  number  and  motion  of  those  new  Planets" 
(50). 

Georgio  Baglivi  and  Father  Jose  de  Acosta  believed  that  metals  grew 
like  plants  under  the  influence  of  the  planets.  "Mettalls,"  said  de  Acosta, 
"are  (as  plants)  hidden  and  buried  in  the  bowels  of  the  earth,  which  have 
some  conformitie  in  themselves,  in  the  forme  and  maner  of  the  production, 
for  that  wee  see  and  discover  even  in  them  branches  and,  as  it  were,  a 
bodie,  from  whence  they  grow  and  proceede,  which  are  the  greater  veines 
and  the  lesse.  .  .they  are  engendered  in  the  bowels  of  the  earth,  by  the 
vertue  and  force  of  the  Sunne  and  other  planets,  and  in  long  continuance 
of  time  they  increase  and  multiply  after  the  manner  of  plants  .  .  the 
rough  and  barren  earth  is  as  a  substance  and  nutriment  for  mettalls  and 
that  which  is  fertile  and  better  seasoned  a  nourishment  for  plants"  (51, 
86). 

In  the  fifth  edition  of  his  "Cours  de  Chymie,"  Nicolas  Lemery  con 
fused  bismuth  with  zinc.  "Bismuth,"  said  he,  "is  a  Sulphureous  Marcassite 
that  is  found  in  the  Tinn  Mines;  many  do  think  it  is  an  imperfect  Tinn 
which  partakes  of  good  store  of  Arsenick;  its  pores  are  disposed  in  another 
manner  than  those  of  Tinn,  which  is  evident  enough  because  the  Men 
struum  which  dissolves  Bismuth  cannot  intirely  dissolve  Tinn.  There  is 
another  sort  of  Marcassite,  called  Zinch,  that  much  resembles  Bismuth .  .  . 
Marcassite  is  nothing  else  but  the  excrement  of  a  Metal,  or  an  Earth 
impregnated  with  Metallick  parts.  The  Pewterers  do  mix  Bismuth  and 
Zinch  in  their  Tinn  to  make  it  found  the  better"  ( 52 ) , 

In  the  eleventh  edition  of  this  work,  Lemery  said  that  older  writers 
believed  bismuth  to  be  "a  natural  marcasite  or  an  imperfect  tin  found  in 
tin  mines;  but  the  moderns,"  said  he,  ''believe  with  much  likelihood  that 
it  is  a  regulus  of  tin  prepared  artificially  by  the  English;  my  thought  on 
this  subject  is  that  there  is  natural  bismuth,  but  that  it  is  rare,  and  that 


ELEMENTS  OF  THE  ALCHEMISTS  107 

which  is  commonly  brought  us  from  England  is  artificial.  However 
that  may  be,  it  is  certain  that  excellent  bismuth  is  made  with  tin,  tartar, 
and  saltpetre;  some  also  mix  arsenic  with  it"  (30,  53). 

Even  as  late  as  1713  the  "Memoirs  of  the  French  Academy"  contained 
the  statement  that  bismuth  is  composed  of  a  mineral,  crude  sulfur,  mer 
cury,  arsenic,  and  earth;  and  the  pharmacopoeias  of  that  time  contained 
recipes  for  making  it  (7),  Lemery,  for  example,  described  the  following 


The  Alchemist,  by  D.  Teniers  ( 1610-1690) 

method  which  he  said  was  used  in  the  English  tin  mines:  "The  work 
men,"  said  he,  "mix  this  tin  with  equal  parts  of  tartar  and  saltpetre.  This 
mixture  they  throw  by  degrees  into  crucibles  rnade  red  hot  in  a  large 
fire,  When  this  is  melted,  they  pour  it  into  greased  iron  mortars  and  let 
it  cool,  Afterward  they  separate  the  regulus  at  the  bottom  from  the  scoriae 
and  wash  it  well.  This  is  the  tin-glass  [bismuth]  which  may  be  called  the 
regulus  of  tin"  ( 1 3 ) , 

Caspar  Neumann  (1683-1737)  clearly  recognized  bismuth  as  a 
specific  metal  (31 ).  "Bismuth,"  said  he,  "is  extracted  from  its  own  proper 
ore,  which  is  found  most  plentifully  in  Saxony,  near  Schneeberg,  and 
of  which  some  quantities  are  met  with  also  in  Bohemia  and  in  England. 
Many  have  affirmed  that  it  is  an  artificial  composition,  and  accordingly 


108  DISCOVERY  OF  THE  ELEMENTS 

delivered  processes  for  making  it;  of  which  processes  I  tried  those  which 
seemed  to  approach  the  nearest  to  probability.  .  "  By  heating  "four 
ounces  of  English  Tin,  two  ounces  of  white  Arsenic,  one  ounce  of  white 
Tartar,  and  half  an  ounce  of  Nitre,  cemented  and  melted  together"  he 
obtained  "a  Regulus,  weighing  three  ounces  and  three  drams,  so  much 
resembling  Bismuth  as  to  be  easily  mistaken  for  it  by  one  who  had  not 
thoroughly  examined  the  appearance  of  that  semi-metal.  There  are,  how 
ever,  some  differences  in  the  structure  of  the  two.  ...  In  their  intrinsic 
properties  they  are  extremely  different:  Thus  the  counterfeit,  dissolved 
in  Aqua  fortis,  forms  a  bluish  coagulum,  whilst  the  solution  of  the  natural 
Bismuth  continues  uniform  and  limpid;  the  counterfeit,  calcined  and 
mixed  with  sulphur,  exhibits  nothing  of  that  singular  needled  structure 
which  the  natural  assumes  in  the  same  circumstances.  Since  therefore  it 
has  been  reported  that  the  Bismuth  met  with  in  the  shops  is  an  artificial 
production,  and  since  experiment  shows  that  it  is  capable  of  being  imitated 
in  its  external  form  though  not  in  its  qualities,  we  ought  to  be  upon  our 
guard  against  such  an  imposition." 

The  French  chemist  Jean  Hellot  noticed  that  the  tin  smelters  in 
Cornwall  added  natural  bismuth,  instead  of  the  ingredients  recommended 
in  the  pharmacopoeias,  to  make  the  tin  haid  and  brilliant,  and  in  1737  he 
obtained  by  fire  assay  of  a  cobalt-bismuth  ore  a  button  of  the  latter  metal 


In  1753  Claude-Francois  Geoffroy,  a  son  of  Claude-  Joseph  (Geoffroy 
the  Younger),  made  a  thorough  investigation  of  bismuth  (7,  20). 
Since  this  metal  had  not  yet  been  introduced  into  medicine  and  was 
used  only  by  pewterers  for  rendering  tin  whiter  and  more  sonorous,  it 
had  been  neglected  by  most  chemists,  J.  H.  Pott,  however,  had  investi 
gated  it  and  published  his  "Exercitationes  chymicas  de  Wismutho,"  and 
C.-F  Geoffroy  first  repeated  the  experiments  of  this  famous  German 
chemist.  Although  Pott  had  stated  that  bismuth  loses  Vss  of  its  weight 
when  calcined  in  an  open  fire,  Geoffroy  found  that  the  weight  increased 
instead,  and  that,  after  the  calx  had  once  been  formed,  no  amount  of 
heat  caused  any  further  increase. 

Knowing  that  lead  behaved  similarly,  Geoffroy  sought  for  other  points 
of  resemblance  between  the  two  metals.  Although  it  had  long  been 
assumed  that  lead  was  the  only  metal  suitable  for  the  cupellation  of 
silver  and  gold,  an  artist  had  informed  Charles  -Frangois  de  Cisternay  du 
Fay  in  1727  that,  if  the  gold  contained  certain  impurities  such  as  emery 
it  was  necessaiy  to  cupel  it  with  a  large  quantity  of  bismuth.  Pott  and 
Geoffroy  both  found  that  bismuth  can  also  be  used  in  the  cupellation  of 
silver.  Although  Pott  had  stated  that  bismuth  is  not  combustible, 
Geoffroy  saw  it  burn  with  its  characteristic  blue  flame  (54).  He  found  ten 


ELEMENTS  OF  THE  ALCHEMISTS  109 

points  of  similarity  between  bismuth  and  lead  but  nevertheless  dis 
tinguished  clearly  between  them  and  closed  with  the  words  "In  a  second 
Memoir  I  shall  ascertain  whether  or  not  this  analogy  holds  on  treating 
these  two  substances  with  acids  and  different  salts"  (54)  Because  of 
his  premature  death  in  1753,  G  -F.  Geoffroy  was  unable  to  complete  this 
second  memoir. 

In  his  "Elements  of  the  Art  of  Assaying  Metals/'  Johann  Andreas 
Cramer  pointed  out  the  close  association  of  bismuth  with  arsenic  and 
cobalt.  "Every  ore  of  Bismuth,"  said  he,  "as  is  shewn  by  the  chemical 
analysis,  is  reduced  to  the  State  of  Ore  by  Arsenick:  For  this  goes  out  of 
it  by  Sublimation.  You  find  in  the  same  Ore  that  Kind  of  Earth  that 
gives  an  azure  Colour  to  Glasses,  of  which  we  have  already  spoken  in 
the  Article  of  Cobalt.  Whence  it  is  evident  that  the  Ore  of  Bismuth  may 
without  Impropriety  be  called  Cobalt  of  Bismuth;  The  more,  because 
you  will  find  in  any  ore  of  Bismuth  the  same  Principles  as  in  Cobalt,  only 
in  a  different  Propoition"  (55).  This  close  association  of  bismuth  and 
cobalt  in  natuie  made  it  difficult  for  eaily  chemists  to  distinguish  between 
them  (56). 

In  Cromwell  Mortimer's  notes  to  the  second  English  edition  of 
Cramer's  work  there  is  a  description  of  an  ore  sent  from  Cornwall  which 
was  "so  very  rich  of  Bismuth  that,  by  only  holding  a  Piece  with  a  Pair 
of  Tongs  against  a  clear  Fire,  the  melting  Bismuth  will  run  down  as 
soon  and  as  easy  as  cheese  will  drop  in  toasting"  (55). 

Torbem  Bergman  ( 1735-1784 )  stated  that  "Bismuth  is  either  native 
or  mineralized  by  sulfur,  perhaps  also  by  acid  air  [carbon  dioxide].  The 
first  ore  was  found  not  in  Germany,  but  in  Sweden,  especially  at 
Riddarhytta"  (80). 

When  the  Swedish  mineralogist  J.  J.  Ferber  visited  Derbyshire  in 
the  latter  part  of  the  eighteenth  century.,  he  found  that  "Mineralogy  in 
England  is  still  in  its  cradle,  and  it  is  not  long  since  Cornish  miners  threw 
away  the  bizmuth  with  the  refuse,  as  a  substance  perfectly  useless,  and 
they  would  have  remained  in  the  same  error  had  it  not  been  for  Dr. 
Schlosser  of  Amsterdam"  (57). 

PHOSPHORUS* 

In  the  seventeenth  century  there  lived  in  Hamburg  a  merchant  by 
the  name  ot  Hennig  Brand  (or  Brandt),  who  was  apparently  the  first 
man  ever  to  discover  an  element.  Of  course,  gold  and  lead  and  the  other 
metals  and  non-metals  used  in  ancient  civilizations  must  have  been  dis- 

*  See  also  "More  on  the  Discovery  of  Phosphorus,"  Chapter  4,  pp.  121-139. 


110  DISCOVERY  OF  THE  ELEMENTS 

covered  by  somebody,  but  these  great  contributors  to  human  knowledge 
are  as  unknown  today  as  is  that  greatest  of  all  inventors-the  man  who 
made  the  first  wheel. 

Brand  was  a  soldier  in  his  youth,  and  it  is  said  that  later  he  became 
"an  uncouth  physician  who  knew  not  a  word  of  Latin"  (8).  In  spite  of 
this  deficiency  he  married  a  wealthy  wife,  who  honored  him  for  his 
scientific  attainments.  While  endeavoring  to  improve  his  financial  stand 
ing,  he  was  lured  by  the  spell  of  alchemy  to  search  for  the  King  of 
Metals.  No  one  knows  what  led  this  zealous  alchemist  to  hope  that  in 
human  urine  he  might  find  a  liquid  capable  of  converting  silver  into  gold, 
but  it  is  well  known  that  his  queer  experiments  made  in  the  seventeenth 
century1  produced  results  that  were  both  startling  and  strangely  beauti 
ful.  Small  wonder  that  he  was  delighted  with  the  white,  waxy  substance 
that  glowed  so  charmingly  in  his  dark  laboratory.  The  method  of 
obtaining  this  light-giving  element,  which  is  now  called  phosphorus, 
Brand  kept  secret,  but  the  news  of  the  amazing  discovery  soon  spread 
throughout  Germany  (9). 

There  lived  at  that  time  a  famous  chemist,  Johann  Kunckel  ( 1630- 
1702),  a  son  of  an  alchemist  in  the  couit  of  the  Duke  of  Holstein  (10). 
The  younger  Kunckel  studied  pharmacy,  glass-making,  and  assaying, 
worked  in  the  Dresden  laboratory  of  John  George  II,  Elector  of  Saxony, 
taught  chemistry  in  the  famous  medical  school  at  Wittenberg,  and  later 
managed  the  glass-works  in  Beilin  belonging  to  Frederick  William,  the 
Elector  of  Brandenburg.  His  last  years  were  spent  in  the  service  of  King 
Charles  XI  of  Sweden,  who  conferred  on  him  the  titles,  Baron  von  Lowen- 
stern  and  Counselor  of  Metals  (10). 

One  day  Kunckel  proudly  exhibited  to  a  friend  in  Hamburg— much 
as  a  modern  chemist  might  show  a  specimen  of  hafnium  or  rhenium— 
a  phosphorescent  substance.  To  his  great  surprise,  the  friend  had  not 
only  seen  this  substance  before,  but  offered  to  take  Kunckel  to  the  home 
of  the  medical  alchemist,  Dr.  Brand,  to  see  a  still  more  remarkable  sub 
stance  that  shines  spontaneously  in  the  dark.  Brand,  they  found,  had 
given  away  his  entire  supply,  but  he  took  Kunckel  to  the  home  of  a 
friend  to  see  the  wondrous  element. 

Kunckel,  in  the  heat  of  excitement,  wrote  immediately  to  his  friend, 
Dr.  Johann  Daniel  Krafft  of  Dresden.  The  latter,  however,  proved  to  be 
a  false  friend,  for,  without  replying  to  Kunckel's  letter,  he  went  immedi 
ately  to  Hamburg  and  bought  the  secret  from  Brand  for  two  hundred 
thalers.  Just  as  the  transaction  was  being  made,  Kunckel  arrived  on  the 
scene.  All  his  attempts  to  learn  the  secret  process  failed,  but  he  did  find 

t  Most  authors  give  the  date  as  1669,  J.  R.  Partington  however  considers  1674  or 
1675  as  the  correct  date. 


ELEMENTS  OF  THE  ALCHEMISTS 


111 


•      -    '    '^  •  • 


Courtesy  Tenney  L,  Davis 


Johann  Kunckel  von  Lowenstern,  1630-1702.  German  chemist,  pharmacist, 
and  glass  technologist  who  gave  an  early  account  of  phosphorus  and  studied 
the  "aurum  potabile"  or  "drinkable  gold"  of  the  alchemists  (60).  Coun 
selor  of  Metals  under  King  Charles  XI  of  Sweden,  (The  portrait  repro 
duced  herewith  is  the  frontispiece  of  KunckeTs  "Ars  Vitraria  Experimentalist 
published  during  his  lifetime  in  1679). 


112  DISCOVERY  OF  THE  ELEMENTS 

out  that  the  new  luminous  substance,  which  had  come  to  be  known  as 
phosphorus,  had  been  obtained  from  urine  (8). 

Kunckel  then  began  experimenting  with  this  fluid,  and  was  finally 
successful.  Like  Brand,  he  refused  to  reveal  the  method,  giving  as  his 
reason  the  fear  that  dangerous  accidents  with  phosphorus  might  become 
frequent.  According  to  Homberg,  Kunckel's  process  was  essentially  as 
follows:  Fresh  urine  was  evaporated  nearly  to  dryness,  after  which  the 
black  residue  was  allowed  to  putrefy  in  a  cellar  for  several  months.  This 


Robert  Boyle,  1627-1691,  British 
chemist  and  physicist  famous  for  his 
researches  on  gases,  his  an  pump,  his 
early  experiments  on  the  mechanical 
origin  of  heat,  and  his  independent  dis 
covery  of  phosphorous.  One  of  the 
founders  of  quantitative  analysis  See 
alsoref.  (59),  (88),  and '(89) 


material  was  heated,  gently  at  first  and  then  stiongly?  with  twice  its 
weight  of  sand,  in  a  retort  leading  to  a  receiver  containing  water.  After 
the  volatile  and  oily  constituents  had  distilled  over,  the  phosphorus  began 
to  settle  out  in  the  receiver  as  a  white,  waxy  solid.  This  was  the  part  of 
the  process  which  Kunckel  thought  too  dangerous  to  reveal  to  the  public. 
To  prevent  fires  and  explosions,  it  was  necessary  to  remove  the  flame 
as  soon  as  the  phosphorus  began  to  appear,  and  to  keep  the  receiver 
closed  until  it  became  cold  ( 8 ) . 

Kunckel  not  only  prepared  phosphorus,  but  also  cast  it  in  molds  to 
obtain  die  stick  phosphorus  now  familiar  to  all  chemistry  students,  He 
also  introduced  its  use  as  a  medicinal,  and  his  famous  book  on  the  subject 
bears  the  curious  title:  "Treatise  of  the  Phosphorus  Mirabilis,  and  Its 
Wonderful  Shining  Pills"  (JO).  It  is  pleasant  to  know  that  his  phos 
phorus  researches  were  not  without  reward,  for  Duke  Johann  Friedrich 
of  Hanover  paid  him  an  annual  pension  for  the  rest  of  his  life  ( 9 ) . 

According  to  Thomas  Thomson  (11),  Willem  Homberg  purchased 
Kunckel's  secret  of  making  phosphorus  by  giving  in  exchange  the  in- 


ELEMENTS  OF  THE  ALCHEMISTS 


113 


Ambrose  Godfrey  Hanckwitz,  1660-1741.  In  this  portrait 
by  George  Vertue  ( 1718),  the  bust  of  Hanckwitz  is  shown 
surrounded  by  his  apparatus.  At  the  left  are  shown  the 
furnace  and  receiver  used  in  the  manufacture  of  phos 
phorus.  The  molten  product  was  removed  with  a  ladle  to 
the  molds  in  which  it  was  cast  into  sticks,  the  entire  opera 
tion  being  carried  out  under  water.  Flaming  phosphorus 
and  the  phoenix,  emblem  of  fire  and  immortality,  figure 
prominently  in  the  foreground. 


114  DISCOVERY  OF  THE  ELEMENTS 

genious  barometer  invented  by  Otto  von  Guericke,  in  which  a  little  man 
comes  to  the  door  of  his  house  in  dry  weather  and  disci  eetly  retires  within 
as  soon  as  the  air  becomes  moist  (35),  Homberg  had  learned  of  the  new 
"phosphoruses"  through  Christian  Adolph  Balduin  and  Johann  Kunckel 
( Kunkel) .  He  found  Balduin  s  phosphorus  to  be  similar  to  the  Bolognian, 
but  more  feebly  luminous.  "He  bought  it  for  some  other  experiment,  but 
he  had  to  have  that  of  Kunkel,  who  had  a  great  reputation.  He  found 
Kunkel  at  Berlin,  and  fortunately  the  latter  was  seized  with  a  desire  to 
own  Guericke's  little  prophet.  The  bargain  was  soon  concluded  between 
the  two  virtuosos,  and  the  little  man  was  given  in  exchange  for  the 
phosphorus.  It  was  the  phosphorus  from  urine,  now  well  known"  (35). 

It  would  be  unfair  to  conclude  this  brief  account  of  the  discovery 
of  phosphorus  without  mentioning  that  Robert  Boyle,  the  illustrious 
British  pioneer  in  pneumatic  chemistry,  also  discovered  it  independently. 
He  prepared  it  by  a  method  somewhat  resembling  that  of  Kunckel,  but, 
as  Boyle  himself  said,  without  any  previous  knowledge  of  that  process. 
Boyle  was  a  man  of  such  high  integrity  that  one  cannot  doubt  the  truth 
of  his  statement.  Krafft  claimed,  however,  to  have  communicated  his 
process  directly  to  Boyle  (32).  Boyle' s  assistant,  Godfrey  Hanckwitz 
made  phosphorus  on  quite  a  large  scale,  and  exported  it  to  Europe  (12). 
One  of  his  advertisements  reads  as  follows:  "Ambrose  Godfrey  Hanck 
witz,  chemist  in  London,  Southampton  Street,  Covent  Garden,  continues 
faithfully  to  prepare  all  sorts  of  remedies,  chemical  and  galenical.  .  .  . 
For  the  information  of  the  curious,  he  is  the  only  one  in  London  who 
makes  inflammable  phosphorus,  black  phosphorus,  and  that  made  with 
acid,  oil,  and  other  varieties.  All  unadulterated.  .  .  .  Solid  phosphorus, 
wholesale  50s.  an  ounce,  and  retail,  £3  sterling,  the  ounce"  (14). 

In  1737  a  stranger  in  Paris  offered  to  sell  the  secret  process  of  mak 
ing  phosphorus  to  the  Academy  of  Sciences.  After  accepting  the  offer, 
tlie  French  .government  appointed  Jean  Hellot  chairman  of  a  committee 
to  study  the  process,  and  his  detailed  report,  published  in  the  Memoirs  of 
the  Academy  for  1737  and  later  in  P.-J.  Macquer's  textbook  of  chemistry, 
made  the  process  accessible  to  all  chemists  (12,  34),  The  "Dictionnaire 
de  Chymie"  published  in  Yverdon,  Switzerland,  in  1767  states  that  "as 
this  process,  up  to  the  present,  has  been  more  curious  than  useful,  and 
as,  moreover,  it  is  both  costly  and  embarrassing,  I  have  no  knowledge 
whatever  that  any  chemist  repeated  it  then  in  France  except  ML  Rouelle, 
who,,  shortly  thereafter,  opened  his  course  in  chemistry,  in  which  he 
tried  to  make  phosphorus  in  presence  of  his  audience.  I  was  present 
at  his  first  attempt;  M,  Hellot,  who  took  great  interest  in  this  experiment, 
came  also,  and  followed  the  process  throughout  its  entire  duration.  We 
spent  the  night  there,  this  first  operation  failed,  to  tell  the  truth,  because 


ELEMENTS  OF  THE  ALCHEMISTS 


115 


P<ilf!w  ESPRaKI  BPL  -  .IB  «f  :v  -.  -V  n!  '  ••J- 

!^=i^r^:-tSS."VSSr..;;:ji:;fKi  fell:!:^,;'  tVife'V 


fa^^ 
^EM^^^ij^i^^s^Jt^^L.  ^mmfc$!T".< 

~ - ' 


Courtesy  Tenneij  *L.  Davis 

Guillaume-Frangois  Rouelle,  1703-1770.  Parisian  apothecary.  Former 
inspector-general  of  the  pharmacy  at  the  City  Hospital.  Demonstrator  in 
chemistry  at  the  Royal  Botanical  Garden.  Member  of  the  Royal  Acad 
emies  of  Science  of  Paris  and  Stockholm  and  of  the  Electoral  Academy  of 
Erfurt.  Born  in  the  village  of  Mathieu  two  leagues  from  Caen  September 
16,  1703,  died  at  Passy  Aug.  3,  1770.  (Translated  from  the  French 
caption  on  the  frame.)  See  also  ref.  (62), 


116  DISCOVERY  OF  THE  ELEMENTS 

of  a  defect  in  the  retoit,  but  in  the  following  years  M.  Rouelle  succeeded 
a  number  of  times  in  making  phosphorus  in  his  course"  (29,  31).  How 
ever,  phosphorus  is  no  longer  prepared  by  the  unpleasant  method  de 
scribed  above.  In  1769  the  Swedish  scientists  Scheele  and  Gahn  (33) 
found  that  it  is  an  important  constituent  of  bones,  and  in  the  following 
year  Scheele  succeeded  in  isolating  it  from  them  (8,  25,  26,  27),  It 
really  is  strange  that  phosphorus  was  discovered  so  early  in  the  history 
of  chemistry,  for  the  reactions  involved  in  Brand's  method  are  rather 
complex,  and  even  today  this  element  is  not  isolated  with  ease. 

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(46)  VON  LIPFMANN,  E    O,  "Die  Geschichte  des  Wismuts  zwischen  1400  und 

1800,"  Julius  Springer,  Berlin,  1930,  42  pp  n 

(47)  VON  LIPPMANN,  E.  O  ,  "Nachtiage  zur  Geschichte  des  Wismuts,    Chem  -Ztg  , 

57,  4  (Jan.  4,  1933), 

(48)  WATTE,  A  E,,  ref.  (IS),  Vol.  1,  p.  8 

(49)  HOOVER,  H  C.  and  L.  H.  HOOVER,  ref.  (24)  pp.  1-3. 

(50)  BARBA,  FATHER  A   A.,  "The  Art  of  the  Metals/'  S    Mearne,  London,  16745 

pp.  29-30,  90-1. 

( 5J )     DE  ACOSTA,  FATHER  JOSE,  "The  Natural  and  Moral  History  of  the  Indies, 
The  Hakluyt  Society,  London,  1880,  Vol   1,  pp    183-4.    English  translation 
by  Edward  Grimston,  1604. 

(52)  LEMERY,  N,,  "A  Course  of  Chymistry/'  Walter  Kettilby,  London,  1686,  2nd 

English  ed.  from  the  5th  French,  pp.  101-2 

(53)  LEMERY,  N.,  "Cours  de  Chymie/'  Theodoie  Haak,  Leyden,  1716,  llth  ed,, 

pp.  136-7. 

(54)  GEOFFROY,  C.-F    (Geoffrey,  fils),  "Analyse  chimique  du  bismuth,  de  laquelle 

il  r6sulte  une  analogic  entre  le  plomb  et  ce  semimetal,"  Mem  de  I'Acad  Roy 
des  Sciences  de  Paris,  1753,  pp   296-312,  Hist   de  I'Acad,  Rot/ ,  1753,  pp. 
190-4. 

(55)  CRAMER,  J    A.,  "Elements  of  the  Art  of  Assaying  Metals,"  L,  Davis  and  C. 

Reymers,  London,  1764,  2nd  ed,,  pp   161-2. 

(56)  BAUME,  A.,  "Chymie  Experimental  et  Raisonnee,"  P,-F.  Didot  le  ]eune,  Pans, 

1773,  Vol.  2,  pp,  371-2. 

(57)  PINKERTON,  JOHN,  "A  general  collection  of  the  best  and  most  interesting  voyages 

and  travels,"  Longman,  Hurst,  Rees,  and  Orme,  London,  1808,  Vol.  2,  p.  484. 
J.  J.  Ferber's  "Essay  on  the  oryctography  of  Derbyshire  " 

(58)  Basihus  Valentinus,  ref.  (36),  part  2,  p.  314. 

(59)  REILLY,  DESMOND,  "Robert  Boyle  and  his  background,"  J   Chem.  Educ,  28, 

178-83  (Apr.,  1951). 

(60)  HAUSER,  ERNST  A.,  "Aurum  potabile,"  ffcid.,  29,  456-8  (Sept,  1952). 

(61)  WINDERLICH,  RUDOLF,  "History  of  the  chemical  sign  language,"   ibid.,   30, 

58-62  (Feb.,  1953). 

(62)  LEMAY,  PEERRE  and  R.  E,  OESPER,  "The  lectures  of  Guillaume  Frangois  Rou- 

elle,"  ibid.,  31,  338-43  (July,  1954). 

(63)  DAVIS,  TENNEY  L.,  "The  advice  of  Albertus  Magnus  to  the  ambitious  alchem 

ist,"  ibid.,  6,  977-8  (May,  1929). 

(64)  "Journals  of  R,  W.  Emerson,"  Centenary  ed.,  Houghton  Miffiin  Co.,  Boston 

and  New  York,  Vol.  II,  p.  288;  see  also  C,  A.  BROWNE,  "Emerson  and 
chemistry/'  J.  Chem  Educ.,  5,  269-79,  391-403  (Mar.-Apr.,  1928). 

(65)  DUFBENOY,  M.  L.,  and  J.  DUFRENOY,  J.  Chem.  Educ  ,  27,  595-7  (Nov  ,  1950). 

(66)  WALKER,  FREDERIC,  "The  iconoclast,"  ibid.,  8,  885-95  (May,  1931). 

(67)  LEMERY,  N.,  ref.  (52),  "A  Course  of  Chymistry,"  Walter  Kettilby,  London, 

1686,  pp.  48-61. 

(68)  "The  Autobiography  of  Benjamin  Franklin   and  Selections  from  his   Other 

Writings/'  Modern  Library,  New  York,  1932,  p,  213. 


ELEMENTS  OF  THE  ALCHEMISTS  119 

(69)  MAcCuRDY,  EDWARD,  "The  Notebooks  of  Leonardo  da  Vinci,"  Garden  City 

Publishing  Co ,  Garden  City,  New  York,  1941-2,  p.  143. 

(70)  BAILEY,  K    C.,  "The  Elder  Pliny's  Chapters  on  Chemical  Subjects,"  Edward 

Arnold,  London,  1932,  Vol.  1,  p.  101,  Vol.  2,  pp.  75-7,  91. 

( 71 )  GUNTHER,  R.  T  ,  "The  Greek  Herbal  of  Dioscorides,"  Oxford  University  Press, 

Oxford,  1934,  pp    632-3,  642. 

( 72 )  GEOFFROY,  E  -F  ,  "Treatise  of  the  Fossil,  Vegetable,  and  Animal  Substances 

That  Are  Made  Use  of  in  Physick,"  W.  Innys,  R.  Manby  et  al.,  London, 
1736,  pp.  163-7. 

(73)  KOPP,  HERMANN,  ref.  (7),  Vol.  4,  pp.  93-4, 

(74)  MARGGRAF,  A.  S.,  "Chymische  Schriften/'  Arnold  Wever,  Berlin,   1768,  re 

vised  ed.,  Vol  2,  pp.  87-112. 

(75)  GEOFFROY,  E.-F.,  ref.  (72),  pp.  191,  196,  209. 

(76)  KOBELL,   FRANZ  VON,   "Geschichte  der  Mineralogie  von   1650-1860,"   J.   G, 

Gotta,  Munich,  1864,  pp.  5S&-7,  540,  609-10 

( 77 )  LUCAS,  A  ,  "Ancient  Egyptian  Materials  and  Industries,"  Edward  Arnold  and 

Co.,  London,  1934,  2nd  ed.,  pp.  81,  147-8. 

(78)  LIPPMANN,  E.  O.  VON,  ref.  (45),  Vol.  2,  pp.  10-11. 

(79)  SvABj  ANTON  VON,  "Berattelse  om  en  nativ  regulus  antimoni  eller  spetsglas- 

kung,"  Vet.  Acad.  Handl.,  10  (1748),  "Recueil  des  memoires,"  ref.   (21), 
Vol.  1,  pp.  166-72. 

(50)  "Dissertatio  metallurgica  de  minerarum  docimasia  humida;   quam  Prses.   M. 

Torb.  Bergmann  [sic!]  defendet  Petr  Castorin,"  Vestm.  Vpsal ,  1780,  4,  p.  40, 
Crett's  Neueste  Entdeckungen  1,  218-9,  225,  230  ( 1781 ) . 

5 SI )  "La  Santa  Bibha  .    .    .  traducida  de  las  lenguas  originales,  y  cotejada  diligen- 

temente  con  muchas  y  diversas  traducciones,"  Am.  Bible  Soc.,  New  York, 

1246  pp. 
(82)     HASTINGS,  JAMES,   "Dictionary  of  the  Bible/*   Charles  Scribner's   Sons,   New 

York,  1929,  p.  103.     Article  on  Antimony. 
(S3)     "The  Holy  Bible  translated  from  the  Latin  Vulgate  (diligently  compared  with 

the  Hebrew,  Greek,  and  "other  editions,  in  various  languages)    .    .    .   with 

annotations  by  the  Rev.  Dr.  Challoner,"  D.  and  J.  Sadlier  and  Co.,   New 

York  and  Montreal. 

(84)  CHEYNE,  T    K.   and  J.   S.   BLACK,   "Encyclopaedia  Blblica,"  Macmillan   Co., 

New  York  and  London,   1902,  Vol    2,  column  2659.     Article  on  Keren- 
happuch  by  T.  K.  Cheyne 

(85)  Ibid.,  Vol.  3,  columns  3524-5.    Article  on  Paint  by  Stanley  A.  Cook. 

(86)  ADAMS,   FRANK  DAWSON,   "The  Birth   and  Development  of  the   Geological 

Sciences,"  Dover  Publications,  Inc.,  New  York,   1954,  pp.  277-328.     The 
origin  of  metals  and  their  ores. 

(57)     OESPER,  RALPH  E.,  "Edmund  O.  von  Lippmann,"  /.  Chem    Educ.,  13,  535 
(Nov.,  1936). 

(88)  MORE,  L.  T.,  "The  life  and  works  of  the  Honourable  Robert  Boyle,"  Oxford 

University  Press,  London,  New  York,  Toronto,  1944,  313  pp 

(89)  BOAS,  MARIE,  "Robert  Boyle  and  Seventeenth  Century  Chemistry,"  Cambridge 

University  Press,  Cambridge,  England,  1958,  240  pp 


Courtesy  Fisher  Scientific  Co. 

The  alchemist.  The  artist  who  painted  this  scene,  Joseph  Wright  of  Derby 
(1734-1797),  called  it  "The  Alchymist  in  search  of  the  philosopher's  stone 
discovers  phosphorus  and  prays  for  the  successful  conclusion  of  his  operation, 
as  was  the  custom  of  the  ancient  chymical  astrologers."  It  was  first  exhibited 
in  1771,  and  was  engraved  by  William  Pether  in  1775. 


4 


More  on  the  discovery  of  phosphorus 


Although  most  accounts  of  the  discovery  of  phosphorus  are  based 
mainly  on  the  writings  of  Kunckel  von  Lowenstern  and  record 
the  events  essentially  as  they  have  just  been  described,  othei  eat  ly 
records  present  a  somewhat  different  story.  In  1902  Hermann 
Peters,  a  famous  German  historian  of  chemistry  and  pharmacy, 
made  a  thorough  study  of  the  autograph  letters  of  Brand,  Kraft, 
Kunckel,  Homberg,  G  W.  Leibniz,  and  others  which  are  pre 
served  in  the  Royal  Library  at  Hanover,  and  found  that,  although 
the  various  accounts  differ  in  many  respects,  they  all  agree  on  one 
point-  namely,  that  phosphorus  was  originally  discovered  by  Dr. 
Hennig  Brand  of  Hamburg.  Although  most  historical  records 
present  Dr.  Brand  as  an  almost  mythical  character  and  do  not 
even  mention  his  Christian  name,  he  emerges  from  these  rare  old 
letters  as  a  real  human  being. 


L 


n  his  correspondence  with  the  Abbe  Nollet,  Raimondo  di  Sangro 
(1710-1771)  mentioned  the  "perpetual  lamps"  of  Saint  Augustine  (354- 
430),  which  were  sometimes  found  in  sepulchers  of  the  early  Christians. 
Raimondo  di  Sangro  believed  that  these  lamps  contained  phosphorus,  and 
Gmo  Testi  considered  this  obscure  point  in  chemical  history  worthy  of 
further  investigation  (26,  77). 

In  his  "History  of  the  match  industry"  in  the  Journal  of  Chemical 
Education,  M.  F.  Crass,  Jr.,  quoted  Paracelsus's  recipe  for  "the  separation 
of  the  elements  from  watery  substances"  (28,  29}.  Paracelsus's  "icicles 
which  are  the  element  of  fire,"  which  he  apparently  obtained  by  dis 
tillation  of  urine,  may  possibly  have  been  elemental  phosphorus.  If 
that  be  the  case,  it  is  difficult  to  understand  why  they  aroused  so  little 
interest 

Most  authorities  agree  that  the  original  discoverer  of  elemental 
phosphorus  was  the  seventeenth-century  alchemist  and  physician  Hennig 
(or  Henning)  Brand  of  Hamburg.  Gottfried  Wilhelm  Leibniz  (1646- 

EDITOR'S  NOTE-  Readers  who  prefer  a  shorter,  yet  connected,  account  of  the  discovery 
of  the  elements  may  find  it  convenient  to  omit  the  supplementary  information  pro 
vided  in  chapters  2,  4,  6,  8,  10,  12,  14,  15,  17,  and  19. 

121 


122  DISCOVERY  OF  THE  ELEMENTS 

1716)  was  personaUy  acquainted  with  Brand,  corresponded  with  him 
regularly  for  at  least  four  years,  and  wrote  a  history  of  the  discovery  of 
phosphorus.  According  to  this  great  philosopher  and  mathematician, 
Brand  was  living  in  1677  at  the  Michaelisplatz  in  Hamburg,  in  the  newer 
part  of  the  city.  His  wife,  Frau  Margaretha  Brand,  was  proud  of  his 
attainments,  and  the  dates  of  her  letters  show  that  she  lived  to  enjoy 
the  honors  which  resulted  from  his  epoch-making  discovery.  A  stepson 
often  assisted  the  doctor  in  his  experiments,  and  there  were  other  children 
as  well.  Although  Dr.  Brand  was  something  of  a  spendthrift  and 
borrower,  die  family  must  have  lived  comfortably  on  their  income  of  1000 
Reichsthalers  a  year.  Visionary  and  impractical  though  he  was,  his  skill 
in  chemistry  won  the  respect  of  his  contemporaries  at  a  time  when  iatro- 
chemistry  held  the  forefront  in  medical  thought.  Ambrose  Godfrey 
Hanckwitz  once  referred  to  him  as  "old  honest  Brandt  of  Hamburg"  (15). 

When  his  alchemical  experiments  revealed  the  beautiful  light-giving 
element,  Brand  called  it  cold  -fire  ("kaltes  Feuer"),  or,  affectionately, 
"mein  Feuer."  The  luminous  substance  which  Kunckel  subsequently 
exhibited  in  Hamburg  was  "Balduins  phosphorus,"  a  phosphorescent 
calcium  nitrate  which  had  been  prepared  by  distilling  a  solution  of  chalk 
in  nitric  acid  (2,  3,  20).  Brand's  "cold  fire"  interested  Kunckel  greatly, 
and  when  he  wrote  about  it  to  his  friend,  Johann  Daniel  Krafft  (or  Kraft) 
of  Dresden,  the  latter  also  came  to  Hamburg.  They  visited  Brand  and 
suggested  that  they  might  be  able  to  sell  his  secret  to  some  royal  person 
age  for  a  high  price.  According  to  Leibniz,  both  Kunckel  and  Krafft 
learned  the  secret  directly  from  Dr.  Brand  at  that  time  (1,4). 

The  learned  Dr,  Krafft  soon  made  the  new  substance  known  far 
beyond  the  walls  of  Hamburg  as  he  traveled  to  the  Netherlands,  to  Eng 
land,  and  even  to  northern  America  ("dem  mitterndchtlichen  Amerika") 
(4).  In  an  attempt  to  sell  the  secret  process,  he  exhibited  the  cold  fire 
in  the  court  of  the  Great  Elector,  Friedrich  Wilhelm  of  Brandenburg. 
On  April  24, 1676,  at  nine  in  the  evening,  all  the  candles  were  extinguished 
while  Dr.  Krafft  performed  before  a  large  assembly  a  number  of  experi 
ments  with  the  "perpetual  fire."  However,  he  did  not  reveal  the  method 
by  which  it  had  been  prepared. 

In  the  following  spring  Dr,  Krafft  went  to  the  court  at  Hanover, 
where  G.  W.  Leibniz  was  serving  as  librarian  and  historian  under  Duke 
Johann  Friedrich,  and  exhibited  two  little  phials  that  shone  like  glow 
worms.  When  Leibniz  suggested  that  a  large  piece  of  phosphorus  might 
give  enough  light  to  illumine  an  entire  room,  Dr.  Krafft  told  him  that  this 
would  be  impractical  because  the  process  of  preparation  was  too  difficult 
(1).  On  September  15,  1677,  Krafft  performed  some  startling  experi 
ments  with  it  before  Robert  Boyle  and  several  other  members  of  the 


MORE  ON  THE  DISCOVERY  OF  PHOSPHORUS 


123 


Royal  Society.  At  the  request  of  Robert  Hooke,  Boyle  wrote  a  detailed 
report  of  them.  After  the  candles  had  been  removed  to  another  room 
and  "the  windows  closed  with  wooden-shuts,"  Krafft's  precious  little 
specimen  of  phosphorus,  of  the  size  of  two  peas,  was  seen  to  shine 
brightly.  When  Krafft  scattered  tiny  bits  of  it  on  the  carpet,  Boyle  was 
delighted  "to  see  how  vividly  they  shined.  .  .  .  And  these  twinkling 
sparks,  without  doing  any  harm  (that  we  took  notice  of)  to  the  Turky 
Carpet  they  lay  on,  continued  to  shine  for  a  good  while.  .  .  .  Mr.  Kraft 
[sic]  also  calling  for  a  sheet  of  Paper  and  taking  some  of  his  stuff  upon 
the  tip  of  his  finger,  writ  in  large  characters  .  .  .  DOMINI,  .  .  .  which 
.  .  .  shone  so  briskly  and  lookt  so  oddly,  that  the  sight  was  extreamly 
pleasing,  having  in  it  a  mixture  of  strangeness,  beauty,  and  frightful- 
ness  .  .  ."  (23).  One  hundred  and  fifty-seven  letters  from  Krafft  are  still 
preserved  in  the  library  at  Hanover. 


Gottfried  Wilhelm  Leibniz,  1646-1716 

German  mathematician,  philosopher, 
historian,  and  scientist.  Independent 
discoverer  of  the  differential  calculus 
He  was  personally  acquainted  with 
Brand  and  Krafft,  and  wrote  a  detailed 
account  of  the  discovery  of  phosphorus, 
including  biographical  sketches  of 
Brand,  KrafFt,  Kunckel,  and  Becher. 


Courtesy    Mathematics    Dept , 
The  University  of  Kansas 


In  July,  1678,  Leibniz  went  to  Hamburg  and  drew  up  a  contract  be 
tween  Duke  Johann  Friedrich  and  Dr.  Hennig  Brand  according  to  which 
the  latter  was  to  correspond  regularly  with  Leibniz  and  keep  him  in 
formed  about  new  developments  regarding  the  "cold  fire"  The  Duke's 
part  of  the  contz-act  consisted  in  the  promise  to  pay  ten  thalers  a  month, 
with  the  stipulation  that  sixty  thalers,  or  six  months'  allowance,  would  be 
paid  in  advance  for  revealing  the  secret  processes  ( "bei  Communicirung 
der  Composition  und  ander  bereit  habender  Curiositaten")  (1). 


124  DISCOVERY  OF  THE  ELEMENTS 

Shortly  aftei  tins,  Dr.  J  J.  Becher  went  to  Hamburg  and  attempted 
to  engage  Brand  for  the  Duke  of  Meddenburg-Gustrow.  In  tins,  how 
ever,  he  was  intercepted  by  Leibniz,  who  took  Dr.  Brand  back  with  him 
to  Hanover  and  advised  Duke  Johann  Friedrich  that  it  would  be  best  to 
keep  him  at  the  court  or  send  him  to  the  Harz  Mountains  until  the 
secret  processes  had  been  tested.  Leibniz  thought  that  Dr.  Brand  would 
be  able  to  prepare  a  large  quantity  of  phosphorus  in  the  mountains  and 
that  he  might  perhaps  find  the  philosophers'  stone.  Brand  did  not  go  to 
the  Harz,  however,  but  remained  in  Hanover  for  five  weeks,  preparing 
a  fresh  supply  of  phosphorus  outside  the  city  and  showing  Leibniz  the 
secret  process  according  to  the  agreement.  The  latter  also  prepared  a 
quantity  of  phosphorus  and  sent  some  of  it  to  the  physicist  Christian 
Huygens  in  Pans,  who  was  studying  the  nature  of  light  (I,  5).  Thus 
Leibniz  was  the  fourth  person  to  prepare  the  new  element  (Brand,  Krafft, 
Kunckel,  Leibniz )  ( I ) , 

Brand,  however,  was  highly  dissatisfied  with  the  pay  he  had  re 
ceived,  and  wrote  angry  letters  to  Leibniz  claiming  that  it  was  insufficient 
for  his  traveling  expenses  and  the  care  of  his  family  at  home.  Frau 
Margaretha  Brand  also  wrote  angrily  to  Leibniz,  and  her  husband  berated 
Krafft  for  inducing  him  to  place  confidence  in  Leibniz  instead  of  in  Dr. 
Becher.  He  also  accused  Krafft  of  having  received  one  thousand  thalers 
for  the  phosphorus  in  England. 

On  December  24,  1678,  Dr.  Krafft  sent  this  letter  to  Leibniz,  saying, 
"Since  you  mention  having  received  an  angry  letter  from  him  [Brand], 
I  am  sending  you  mine  herewith.  You  may  compare  them  and  see  which 
is  the  prettier"  (I).  Nevertheless,  Leibniz  advised  the  Duke  to  deal 
more  liberally  with  Dr.  Brand,  partly  out  of  sympathy,  and  partly  to 
prevent  him  from  selling  his  secrets  to  others. 

This  tactfulness  calmed  Brand's  wrath,  and  in  1679  he  planned 
another  trip  to  Hanover  to  prepare  phosphorus  on  a  large  scale  and  reveal 
his  other  chemical  secrets.  A  weekly  salary  of  ten  thalers  in  addition  to 
board  and  traveling  expenses  was  agreed  upon,  and  a  later  letter  shows 
that,  on  this  second  tap,  Brand  worked  for  Duke  Johann  Fnedrich  two 
months.  The  last  letter  from  Brand  in  the  Hanover  library  is  dated 
August  23,  1682,  but,  according  to  Leibniz,  he  was  still  living  ten  years 
later  (1,  4).  Hermann  Peters  thought  that  possibly  other  letters  from 
Brand  may  still  exist  in  Hamburg  or  elsewhere. 

Leibniz  communicated  Brand's  method  of  making  phosphorus  to 
Count  Ehrenfried  Walter  von  Tschirahaus  (1651-1708)  in  Paris,  and 
sent  him  a  specimen  by  request.  When  Count  E.  W.  von  Tschirnhaus 
(58)  published  the  Brand-Leibniz  recipe  in  the  history  of  the  Royal 
Academy,  Colbert  recommended  him  for  membership  in  the  French 


MORE  ON  THE  DISCOVERY  OF  PHOSPHORUS  125 

Academy  of  Sciences,  and  on  July  22,  1682,  he  was  elected.  According 
to  Dr.  Peters,  this  recipe  was  also  published  in  the  fifth  edition  of 
Nicolas  L&nery's  "Cours  de  Chymie"  in  1683  ( 1 ) 

When  Krafft  went  to  England,  he  exhibited  phosphorus  in  the  court 
of  Charles  II  and  showed  it  to  the  Honourable  Robert  Boyle  (19  4,  6,23}. 
The  great  British  scientist  then  prepared  it  by  a  slightly  different 
method  and  studied  its  properties  more  thoroughly  than  did  any  other 
chemist  of  the  seventeenth  century  (1). 

When  Willem  Hombeig  defended  Kunckel's  claim  to  the  re 
discovery  of  phosphorus  after  the  original  secret  process  had  been  lost  to 
the  world,  Leibniz  strove  to  defend  the  rights  of  Dr  Brand  and  stated 
emphatically  that  the  real  discoverer  of  phosphorus  was  still  living  long 
after  Krafft  and  Kunckel  had  made  the  element  known,  and  that  he  used 
to  complain  bitterly  about  his  false  treatment  (I).  Although  Krafft 
published  his  recipe  in  1679,  Brand  was  still  living  in  1692,  and  even 
by  1710  Leibniz  had  heard  no  report  of  his  death.  A.  Godfrey  Hanck- 
witz  once  paid  the  following  tribute  to  the  great  Hamburg  chemist: 

...  as  all  things  have  their  period  so  has  also  the  vitalis  lucula  (scintilla, 
spark)  by  approaching  age.  By  (in  the  case  of)  this  urosophus  Brandt,  it  daily 
lessened  and  wore  off,  till  at  last  in  the  midst  of  his  best  experiments  it  e'en 
quite  extinguished  His  fine  stare  fire,  which  through  art  he  produced,  remained 
for  his  memory  longer  with  us  than  himself  .  .  .  and  shined  longer  than  his 
flammula  vitse,  that  in  time  of  his  best  occupation  did  tain  and  return  to  its  fiery 
sphere  His  acquaintances  and  confidents  would  feign  (if  wishes  would  have 
done  it)  have  retarded  his  decrease  to  set  it  farther  off  .  .  (15). 

Robert  Hooke  and  his  contemporaries,  recalling  the  animal  origin  of 
phosphorus,  had  several  "disputes,  whether  there  were  any  such  thing  as 
flammula  vitse:  and  it  was  conceived  by  some  that  the  experiments  of 
phosphorous  [sic]  plainly  proved  such  a  flammula  as  being  extracted 
either  immediately  out  of  the  blood  or  mediately  out  of  the  urine"  (30). 
The  great  Dutch  physician  and  chemist  Herman  Boerhaave  (1668-1738), 
in  speaking  to  his  students  concerning  some  of  the  errors  into  which 
chemists  had  fallen,  said  "One  has  therefore  made  of  the  human  body  a 
laboratory  of  chemistry.  ...  All  of  these  errors  have  been  carried  to 
the  point  that  an  otherwise  excellent  man  has  dared  to  propose  that 
the  body  contains  a  lighted  fire,  since  chemistry  has  found  the  means 
of  extracting  the  English  phosphorus  from  urine  with  the  aid  of 

fire"  (46). 

According  to  Leibniz,  Brand  was  not  secretive,  but,  on  the  contrary, 
gave  over  the  process  too  readily  to  Krafft  and  Kunckel  in  return  for 
some  little  gifts  and  the  promise  of  larger  payments  (1,  4).  When 
Kunckel  tried  out  the  process  at  home,  his  first  attempts  were  unsuccess- 


126  DISCOVERY  OF  THE  ELEMENTS 

ful.  His  complaining  letters  to  Brand  brought  him  no  further  information, 
however,  for  the  Hamburg  chemist  had  soon  regretted  his  poor  bargain. 
In  the  meantime  Kunckel  experimented  by  a  trial-and- error  method,  and, 
since  he  had  seen  the  process  and  was  familiar  with  Brand's  distillation 
apparatus,  he  finally  succeeded  in  correcting  his  own  mistake.  He  then 
had  the  audacity  to  claim  the  discovery  for  himself  (1,4). 

In  a  letter  to  Brand  written  from  Wittenberg  on  June  25,  1676, 
Kunckel  asked  him  directly  for  the  details  of  preparation,  suggesting 
that  the  recipe  might  be  worded  so  obscurely  as  to  be  meaningless  to 
others,  and  assuring  him  that  there  would  be  no  danger  of  any  one  else 
opening  the  letter.  He  complained  because  Brand  had  given  some  phos 
phorus  to  Krafft  and  the  chaplain  of  the  Pest  House,  and  begged  him 
to  give  no  more  of  it  to  any  one  else.  Kunckel  modified  the  Brand  process 
a  little  by  adding  sand  to  the  urine  before  distilling,  In  June,  1676,  he 
told  his  friend,  G.  C.  Kirchmaier,  professor  of  chemistry  at  Wittenberg, 
about  the  new  process,  and  the  latter  published  a  paper  on  it.  Whether 
Kunckel  ever  prepared  the  new  element  on  a  large  scale  or  not  is  not 
known,  but  at  the  end  of  his  history  of  phosphorus  he  wrote,  "However, 
I  am  not  making  it  any  more,  for  much  harm  can  come  of  it"  (2,  3). 

Dr,  Heimann  Peters  concluded  from  a  study  of  these  old  letters 
that  Kunckel  did  not  rediscover  phosphorus,  but  merely  made  a  little  of 
it  by  Brand's  method,  and  that,  even  without  Kunckel,  phosphorus  would 
have  remained  known  to  the  world  through  the  efforts  of  Krafft,  Leibniz, 
and  Boyle  (I). 

In  1726  W.  Derham  published  a  book  entitled  "Philosophical  Experi 
ments  and  Observations  of  the  Late  Eminent  Dr.  Robert  Hooke,  F.R.S. 
and  Geom.  Prof.  Gresh  and  Other  Eminent  Virtuoso's  in  His  Time,"  in 
which  he  included  a  detailed  description  of  Brand's  process  of  making 
phosphorus  (20).  Under  the  title  TPhosphoros  Elementaris,  by  Dr. 
Brandt  of  Hamburgh/'  Derham  wrote: 

"Take  a  Quantity  of  Urine  (not  less  for  one  Experiment  than  50 
or  60  Pails  full);  let  it  lie  steeping  in  one  or  more  Tubs,  ,  .  .  till  it 
putrify  and  breed  Worms,  as  it  will  do  in  14  or  15  days.  Then,  in  a  large 
Kettle,  set  some  of  it  to  boil  on  a  strong  Fire,  and,  as  it  consumes  and 
evaporates,  pour  in  more,  and  so  on,  till,  at  last,  the  whole  Quantity  be 
reduced  to  a  Paste  .  .  .  and  this  may  be  done  in  two  or  three  Days,  if  the 
Fire  be  well  tended,  but  else  it  may  be  doing  a  Fortnight  or  more.  Then 
take  the  said  Paste,  or  Coal;  powder  it,  and  add  thereto  some  fair  Water, 
about  15  Fingers  high  .  ,  .;  and  boil  them  together  for  Va  of  ar*  Hour. 
Then  strain  the  Liquor  and  all  through  a  Woolen  Cloth  ...  the  Liquor 
that  passes  must  be  taken  and  boil'd  till  it  come  to  a  Salt,  which  it 
will  be  in  a  few  Hours.  Then  take  off  the  Caput  Mortuum  (which  you 


MOKE  ON  THE  DISCOVERY  OF  PHOSPHORUS  127 

have  at  any  Apothecary's,  being  the  Remainder  of  Aqua  Fortis  from 
Vitriol  and  Salt  of  Niter)  and  add  a  Pound  thereof  to  half  a  Pound  of 
the  said  Salt,  both  of  them  being  first  finely  pulverized.  And  then  for 
24  Hours  steep'd  m  the  most  rectify'd  Spirit  of  Wine,  two  or  three  Fingers 
high,  so  as  it  will  become  a  Kind  of  Pap. 

"Then  evaporate  all  in  warm  Sand,  and  there  will  remain  a  red,  or 
reddish,  Salt.  Take  this  Salt,  put  it  into  a  Retort,  and,  for  the  first  Hour, 
begin  with  a  small  Fire,  more  the  next,  a  greater  the  3d,  and  more  the 
4th;  and  then  continue  it,  as  high  as  you  can,  for  24  Hours.  Sometimes, 
by  the  Force  of  the  Fire,  24  Hours  proves  enough;  for  when  you  see  the 
Recipient  white,  and  shining  with  Fire,  and  that  there  are  no  more 
Flashes,  or,  as  it  were,  Blasts  of  Wind,  coming  from  Time  to  Time  from 
the  Retort,  then  the  Work  is  finished.  And  you  may,  with  Feather, 
gather  the  Fire  together,  or  scrape  it  off  with  a  Knife,  where  it  sticks/' 

Derham  said  of  this  phosphorus,  "I  saw  some  of  it,  press'd  with  a 
Quill  that  was  cut,  and  it  fired  Gun-powder  about  it.  Mr.  Concle 
[Kunckel?]  writ  also  with  it  on  Paper,  and  the  Letters  all  shined  in  the 
Dark.  .  .  .  My  Author  says  he  had  once  wrapp'd  up  a  Knob  in  Wax, 
at  Hanover,  and  it  being  in  his  Pocket,  and  he  busy  near  the  Fire,  the 
very  Heat  set  it  in  Flame,  and  burn'd  all  his  Cloaths,  and  his  Fingers 
also;  for  though  he  rubbed  them  in  the  Dirt,  nothing  would  quench  it, 
unless  he  had  had  Water,  he  was  ill  for  15  Days,  and  the  Skin  came 
off.  .  .  ." 

The  following  incident  related  by  Nicolas  Lemery  illustrates  the 
carelessness  of  early  chemists  in  handling  this  dangerously  flammable 
element.  "After  some  Experiments,"  said  he,  "made  one  day  at  my  house 
upon  the  Phosphorus,  a  little  piece  of  it  being  left  negligently  upon  the 
Table  in  my  Chamber,  the  maid  making  the  bed  took  it  up  in  the  bed 
clothes  she  had  put  upon  the  Table,  not  seeing  the  little  piece:  the  person 
who  lay  afterwards  in  the  bed,  waking  at  night  .  ,  .  ,  perceived  that  the 
coverlid  was  on  fire"  ( SI ) . 

In  his  article  entitled  "The  aerial  noctiluca,"  Robert  Boyle  mentioned 
that  "the  experienced  chymist  Mr,  Daniel  Krafft  had,  in  a  visit  that  he 
purposely  made  me?  shewn  me  and  some  of  my  friends,  both  his  liquid 
and  consistent  phosphorus.  .  .  ."  In  return  for  some  information  about 
"uncommon  mercuries,  ...  he  [Krafft],  in  requital,  confest  to  me  at 
parting,  that  at  least  the  principal  matter  of  his  phosphorus's  was  some 
what  that  belonged  to  the  body  of  man  .  .  /'  (6,  19).  On  September  30, 
1680,  Boyle's  efforts  to  prepare  the  luminous  element  were  crowned  with 
success,  and  two  weeks  later  he  deposited  his  recipe  with  the  secretaries 
of  the  Royal  Society,  who,  however,  did  not  open  it  until  after  he  had 
died  in  1691  (7). 


128 


DISCOVERY  OF  THE  ELEMENTS 


Boyle  s  assistant,  A.  G.  Hanckwitz  or  Hanckewitz  (1660-1741),  was 
therefore  able  to  develop  the  piocess  on  a  commercial  scale,  improve  it, 
and  export  phosphorus  to  the  continent  (8,9,17).  Hanckwitz  had  been 
brought  over  from  Germany  at  an  early  age  by  his  honored  master.  He 
later  built  furnaces  and  stills  in  Maiden  Lane,  and  traveled  through  the 


Ambrose  Godfrey,  According  to  Ince 
(Ref,  15)  tins  represents  Ambrose  God 
frey  Hanckwitz,  but  according  to  Pilcher 
( Ref.  22 )  it  is  Hanckwitz's  son,  Ambrose 
Godfrey  ( 1685-1756 ) .  Since  the  portrait 
was  made  from  life  in  1738  it  must 
represent  the  son. 


Netherlands,  France,  Italy,  and  Germany,  He  founded  a  famous  phar 
maceutical  firm  in  London,  and  so  great  was  his  fame  that  a  letter  once 
came  to  him  safely  from  Berlin  addressed  simply,  "For  Mr,  Godfrey, 
famous  Chymist  in  London"  (15).  He  was  known  in  England  simply 
by  the  name  Ambrose  Godfrey,  the  German  surname  being  reserved  for 
formal  occasions, 

The  letters  which  constitute  his  correspondence  with  Sir  Hans  Sloane 
from  1721  to  1733  are  still  preserved  in  the  British  Museum  (IS),  and  in 
1858  Joseph  Ince  wrote  an  interesting  biographical  sketch  of  Hanckwitz 
based  on  correspondence,  diaries,  and  notes  (15).  According  to  Caspar 
Neumann,  "Mr.  Godfrey  himself  .  .  ,  was  once  in  danger  of  his  life  from 
[phosphorus],  his  hand  being  burnt  so  terribly  that  for  a  time  he  was  out 
of  his  senses,  and  for  three  days  lay  in  exquisite  pain,  as  if  his  hand  had 
been  constantly  in  a  fire"  (21).  In  spite  of  all  his  dangerous  experiments, 
this  great  disciple  of  Robert  Boyle  lived  to  be  an  octogenarian.  He  died 
on  January  15,  1741,  and  was  survived  by  three  sons,  Boyle,  Ambrose, 
and  John  Godfrey,  all  of  whom  shared  their  father's  interest  in  science, 


MORE  ON  THE  DISCOVERY  OF  PHOSPHORUS 


129 


Hanckwitz  kept  his  recipe  for  phosphorus  a  profound  secret,  and, 
even  in  the  article  which  he  published  in  1733,  forty  or  fifty  years  after 
leaving  Boyle's  laboratory,  gave  only  an  obscure  description  of  the 
process  (8, 10).  The  sons  evidently  adopted  the  same  policy,  for  one  of 
them  wrote: 

As  to  the  phosphorus  made  of  urine  called  Kunckel's,  we  have  it  described 
by  the  Honourable  Mr.  Boyle,  Mons  Hombeig,  and  others.  But  I  shall  beg  to 
be  excused  f 01  not  discovering  the  process  how  I  prepare  it,  or  from  giving  any 
farther  light  into  its  production  than  what  was  done  by  my  father,  before  the 
Royal  Society,  in  the  year  1733  (16) . 

Yet  only  two  years  after  this  obscure  and  vague  description  of  the 
process  was  published,  the  aged  Hanckwitz  allowed  Dr.  J.  H.  Hampe, 
the  court  physician,  to  coax  him  into  revealing  the  secret  (8).  Two  cen 
turies  later  Dr.  Max  Speter  found  this  long-lost  recipe  in  an  unexpected 
place.  In  the  published  correspondence  of  the  Counselor  of  Mines, 
Johann  Friedrich  Henckel  (or  Henkel)  of  Freiberg  (1679-1744),  there 


Max  Speter,  1883-1942,  Transylvaman 
inventor  and  historian  o£  chemistry 
Author  of  many  articles  on  Boerhaave, 
Geoffrey  the  Elder,  Marggraf,  Black 
and  Lavoisier.  Contributor  to  "Das 
Buch  der  grossen  Chemiker,"  In  1929 
he  found  the  Boyle-Hanckwitz  recipe  for 
phosphorus,  after  it  had  been  kept 
secret  for  more  than  two  centuries  (25). 


appears  a  letter  from  Dr.  Hampe  written  in  London  on  August  29,  1735 
(8,  11).  In  reply  to  Henckel's  inquiries  regarding  Hanckwitz  and  the 
secret  process,  Dr,  Hampe  wrote  that  Boyle's  famous  assistant  was  still 
living,  but  so  forgetful  because  of  advanced  age  that  little  could  be  learned 
from  him.  Nevertheless,  through  diligent  questioning  of  the  old  man,  he 


130  DISCOVERY  OF  THE  ELEMENTS 

had  succeeded  in  getting  the  essential  details  of  the  phosphorus  recipe 
which  Henckel  had  requested.  Dr.  Hampe  asked  Henckel  to  write  him 
about  any  difficulties  that  might  arise  in  his  attempts  to  make  phosphorus, 
in  order  that  the  aged  Hanckwitz  might  be  further  questioned  if  necessary. 

From  this  letter  it  appears  that  "the  true  key"  to  the  process,  which 
consisted  in  distilling  a  mixture  of  solid  and  liquid  excrement,  "was,  above 
all  else,  that  everything  be  done  under  water;  especially  while  pouring 
it  into  the  molds  and  while  cutting  it,  enough  water  must  always  be  at 
hand"  (8,  II).  To  avoid  the  necessity  of  redistillation,  or  rectification, 
Hanckwitz  pressed  the  phosphoius  through  leather,  being  carefull  to  keep 
it  under  water.  In  a  second  letter  written  on  September  9  of  the  same 
year,  Dr,  Hampe  gave  Henckel  further  information  about  the  process. 
On  November  15  he  asked  Henckel  not  to  divulge  the  secret  to  any  one 
else  and  suggested  that  they  keep  each  other  informed  about  the 
experiments  with  phosphorus  (S). 

Henckel  had  learned  the  details  of  Kunckel's  method  of  preparing 
it  as  eaily  as  1731  from  Johann  Lmck,  an  apothecary  in  Leipzig,  In  his 
letter  of  May  29,  1731,  Linck  stated  that  a  better  method  was  being  used 
in  England  by  Hanckwitz,  but  that  he  did  not  know  the  details  (8,  II). 
f  Hanckwitz,  however,  like  his  contemporaries,  had  entirely  incorrect 
'views  as  to  the  chemical  nature  of  phosphorus.  'Its  principal  Contex 
ture/'  said  he,  "is  found  to  consist  of  a  subtile  Acid  concentrated  by  the 
Salt  of  Urine,  and  of  a  fat  depurated  Oil  .  .  .  The  Phlogistic  Part  is 
so  slightly  connected  with  the  other  Principles,  that  the  least  Motion, 
Friction,  or  Warmth,  sets  it  on  fire.  .  .  .  Phosphorus  may  be  called  an 
urinous  Soap,  as  it  consists  of  the  saline  and  oleaginous  Parts  of  the 
Urine.  .,,  .  In  regard  to  the  Parts  whereof  Phosphorus  consists,  it  may 
be  considered  as  the  Soot  of  a  deflagrated  Oil;  and  so  may  every  com 
bustible  Substance  be  looked  upon  as  a  Kind  of  Phosphorus,  as  con 
sisting  of  inflammable  Materials.  .  ,  .  Phosphorus  is  more  immediately 
compounded  of  a  Salt  tending  to  the  Nature  of  Sal  Ammoniac,  of  an 
urinous  Salt,  of  an  Acid,  and  an  oily  Phlogiston,  with  a  subtile  Earth.  .  .  . w 
He  also  stated  that  glowworms  "seem  to  have  Phosphorus  lodged  in  their 
bodies."  Hanckwitz  claimed  that  Kunckel,  Krafft,  and  Brand  had  been 
able  to  obtain  only  "unctuous  and  opaque"  phosphorus,  whereas  his  was 
"hard,  transparent,  and  glacial"  (10). 

Another  of  the  early  experimenters  with  phosphorus  was  the  Abb6 
J.-A,  Nollet,  who  watched  Jean  Hellot  and  others  demonstrate  its  prop 
erties  before  the  French  Academy  of  Sciences  in  1737  (32),  The  pro 
cedure  was  described  in  detail  in  the  Memoirs  of  the  Academy  of  Sciences 
for  that  year  and  later  in  P.-J.  Macquer's  "Elements  of  the  Theory  and 
Practice  of  Chymistry."  Even  in  the  eighteenth  century,  chemists  had 


MORE  ON  THE  DISCOVERY  OF  PHOSPHORUS 


131 


From  FerchTs  Apotheker-Kalender  for  1932 

Courtesy  Mr.  Arthur  Nemayer, 

Buchdruckerei  und  Verlag,  Mittenwald,  Bavaria. 

Johann  Heinrich  Linck,  1675-1735.  Leipzig  apothecary 
who  communicated  Kunckel's  method  of  preparing  phos 
phorus  to  J.  F.  Henckel.  The  "Golden  Lion"  pharmacy 
was  in  possession  of  the  Linck  family  for  three  generations, 
and  their  museum  of  natural  history  and  art  was  known 
throughout  all  Germany. 


a  completely  erroneous  idea  of  its  nature.  "Almost  all  the  Chymistv 
said  Macquer,  "consider  Phosphorus  as  a  substance  consisting  of  the 
Acid  of  Sea-Salt  combined  with  the  Phlogiston,  in  the  same  manner  as 
Sulphur  consists  of  the  Vitriolic  Acid  combined  with  the  Phlogiston"  (33). 
This  conception  was  based,  according  to  Macquer,  on  the  presence  of 


132  DISCOVERY  OF  THE  ELEMENTS 

salt  and  phlogiston  (carbonaceous  matter?)  in  the  urine  from  which 
phosphorus  is  prepared  and  on  the  fact  that  phosphoric  acid,  like  hydro 
chloric,  throws  down  a  precipitate  with  silver  nitrate  (33). 
r  In  1743  A.  S.  Marggraf,  a  student  of  Henckel,  found  a  much  better 
way  of  preparing  this  element  from  urine  (12,  13,  14,  24)  and,  since  the 
phosphorus  business  was  no  longer  as  profitable  as  it  had  been,  he 
promptly  published  the  process.  According  to  Marggraf,  the  new 
method  had  been  suggested  by  Henckel's  statement  that,  when  the  "calx 
of  lead"  was  digested  with  sal  ammoniac,  potassium  carbonate,  and  old 
urine,  and  then  distilled,  a  good  grade  of  phosphorus  could  be  obtained. 
According  to  J  Mielcke,  the  rmciocosmic  salt,  NaNH4HPO4  4HjO,  in  the 
urine  was  converted  by  heating  into  sodium  metaphosphate,  NaPOs.  In 
the  meantime  the  potassium  carbonate  and  carbon  reduced  the  lead 
chloride  and  lead  oxychloride  to  lead,  after  which  the  carbon  and  lead 
reduced  the  sodium  metaphosphate  to  sodium  pyrophosphate  and 
phosphorus  (1,2).  Dr.  Speter  also  studied  the  correspondence  between 
Marggraf  and  Henckel  regarding  this  interesting  method  of  preparing 
phosphorus. 

Marggraf  tried  in  vain  to  prepare  phosphorus  without  urine.  When 
he  used  mixtures  of  various  chlorides  with  "vegetable  coals,  and  even 
animal  matters  such  as  oil  of  hartshorn,  human  blood,  etc.,"  all  his 
attempts  failed  When  he  sepaiatecl  some  microcosmic  salt  from  urine, 
however,  mixed  the  salt  with  lampblack,  and  distilled  the  mixture,  "he 
obtained  from  it  a  considerable  quantity  of  very  fine  phosphorus  .  .  ,  , 
whence  he  concluded  that  in  this  Saline  matter  resides  the  true  Acid 
,that  is  fit  to  enter  into  the  composition  of  phosphorus"  (33), 

In  1688  Bernhard  Albinus  ( Weiss )  mentioned  the  presence  of  phos 
phorus  in  the  ash  of  mustard  and  cress  (34).  In  1743  Marggraf  prepared 
it  from  wheat  and  mustard  (35).  "In  order  to  demonstiate  by  experi 
ment,"  said  he,  "that  the  vegetables  we  en]oy  every  day  or  occasionally 
also  contain  that  which  is  necessary  for  the  production  of  the  phosphorus, 
I  found  in  Albinus'  Dissertation  on  Phosphorus  as  well  as  on  page  477  of 
the  celebrated  Hofmann's  [Friedrich  Hoffmann's]  notes  to  Poterius 
that  the  seeds  of  black  and  white  mustard  and  of  cress  yield  phosphorus. 
Since  I  myself,  however,  still  had  no  experience  with  it,  yet  found  in 
Professor  Pott's  Collegio  Mscpto  on  the  first  edition  of  Boerhaave's 
Chemistry  that  wheat,  rye,  and  other  similar  grains  yield  phosphorus, 
I  made  the  following  experiments  .  .  ."  (35), 

When  Marggraf  distilled  the  seeds  of  white  and  black  mustard, 
garden  cress,  pepper,  and  wheat,  he  obtained  phosphorus  from  each  of 
them  except  the  pepper.  Although  Albinus  had  added  sand,  Marggraf 
found  this  to  be  unnecessary.  For  the  sake  of  economy,  Marggraf  used 


MORE  ON  THE  DISCOVERY  OF  PHOSPHORUS  133 

pepper  fiom  which  the  essential  oil  had  previously  been  distilled  (35). 
When  he  found  that  microcosmic  salt  could  be  reduced  to  phosphorus, 
he  became  curious  to  know  the  source  of  this  salt  in  human  urine.  Since 
he  found  higher  concentrations  of  microcosmic  salt  and  phosphoric  acid 
in  the  urine  in  the  summer  (when  people  eat  more  garden  products  such 
as  mustard  and  cress),  he  thought  it  probable  that  these  might  be  the 
source  of  the  microcosmic  salt  (36').  Although  the  modern  chemist  has 
simple  qualitative  tests  for  phosphates,  Marggraf  and  his  contemporaries 
were  obliged  to  carry  out  the  much  more  difficult  process  of  liberating 
elemental  phosphorus  in  order  to  detect  its  presence 

Since  plants  and  animals  are  able  to  concentrate  phosphorus  in 
their  tissues.,  and  since  these  tissues  contain  their  own  reducing  agents, 
E.  B.  R,  Prideaux  does  not  consider  it  surprising  that  physicians  and 
pharmacists  of  the  seventeenth  and  eighteenth  centuries  first  prepared 
this  element  from  substances  of  vegetable  and  animal  origin  (36), 

Lavoisier  said  that  "Phosphorus  is  met  with  in  almost  all  animal  sub 
stances  and  in  some  plants  which,  accordmg  to  chemical  analysis,  have 
an  animal  nature.  ,  .  .  The  discoveiy  that  M.  Hassenfratz  has  made  of 
this  substance  in  wood  charcoal  would  make  one  suspect  that  it  is 
commoner  in  the  vegetable  realm  than  has  been  thought;  this  much  is 
certain:  that,  when  properly  treated,  entire  families  of  plants  yield  it" 
(37),  Apothecary  J,  K.  F.  Meyer  of  Stettin  wrote  in  1784  that  he  had 
observed,  several  years  previously,  a  permanent  green  color  in  the 
essences  he  prepared  by  digesting  green  herbs  in  copper  vessels  He 
concluded  that  phosphates  in  the  leaves  had  reacted  with  the  copper 
to  form  copper  phosphate  (38). 

William  Lewis  stated  in  1759  that  the  ash  of  bones  and  horn 
resembles  chalk  and  "the  earth  of  the  shells  of  sea-fishes  ,  ,  .  in  being 
easily  soluble  in  nitrous  [nitric],  marine,  and  vegetable  acids,  and  not 
in  the  vitriolic."  The  only  difference  he  was  able  to  observe  between 
the  calcareous  earth  from  shells  and  the  bone  ash  was  that  the  latter  is 
"not  changeable  by  fire  into  Lime:  How  strongly  soever  the  earth  of 
Bones  and  Horns  be  calcined,  it  continues  insipid  and  gives  no  manifest 
impregnation  to  water"  (39). 

When  J.  G.  Wallerius  analyzed  eggs,  bone,  and  other  animal  sub 
stances  in  1760,  he  detected  lime,  and  had  a  vague  idea  that  they  also 
contain  certain  other  earths.  In  a  footnote  to  this  paper  in  the  Neues 
chemisches  Archiv,  Crell  stated,  "Hr.  W.  did  not  yet  know  the  nature 
of  the  animal  earth  which  the  unforgettable  Scheele  made  known  to  us: 
that  is?  that  it  consists  of  lime  and  phosphoric  acid"  (40).  In  1769  C.  W, 
Scheele  and  J.  G.  Gahn  discovered  that  phosphorus  is  an  important 
constituent  of  bone.  Although  some  historians  of  chemistry  have 


134  DISCOVERY  OF  THE  ELEMENTS 

attributed  this  discovery  to  Gahn  or  Scheele  alone,  Dr.  Max  Speter  proved 
from  Gahn's  own  notes  that  both  had  a  part  in  it  (41 ). 

In  his  Chemisches  Journal  Lorenz  von  Crell  mentioned  a  rare 
publication  announcing  this  discovery.  "In  the  medical  commentaries 
of  a  society  of  physicians  at  Edinburgh  I  found  in  the  first  issue  of  the 
third  part  (p.  97  ff.  of  the  German  translation,  Altenb.  1776)  a  report 
by  Hrn.  D.  Heinrich  Gahn  of  Stockholm  of  how  one  can  obtain  a  phos 
phorus  from  the  bones  of  animals  and  especially  from  the  hartshorn.  I 
searched  for  a  more  detailed  account  of  this  wonderful  discovery  of  Herr 
Gahn's.  Except  for  the  remark  m  C.  W.  Scheele  s  investigation  of  fluor 
spar  that  it  has  recently  been  discovered  that  the  earth  in  bones  or  horns 
is  lime  saturated  with  phosphoric  acid,  all  my  searching  was  in  vain. 
In  the  meantime,  since  this  process  of  working  up  bones  to  obtain  the 
phosphorus  seemed  to  me  to  belong  to  the  masterpieces  of  chemical 
decomposition,  I  repeated  the  experiment  according  to  the  instruction 
in  the  aforementioned  book,  and,  to  my  great  pleasure,  found  it  to  be 
true"  (42}.  The  "Heinrich  Gahn"  mentioned  by  von  Crell  was  probably 
J.  G.  Gahn's  brother,  Henrik  Gahn,  assessor  in  the  medical  school. 

Even  to  J.  G.  Gahn  and  Scheele,  phosphorus  was  a  rarity.  When 
Scheele  first  read  the  English  translation  of  his  treatise  "On  air  and  fire," 
he  found  that  Johann  Reinhold  Foister  had  translated  the  word  Gran  as 
ounces  instead  of  grains.  "Nine  ounces  of  phosphorus,"  said  Scheele, 
"I  have  never  yet  seen"  (43). 

Even  in  the  eighteenth  century,  phosphorus  was  still  regarded  as  an 
animal  production,  "The  phosphorus,  made  of  animal  parts/'  wrote 
C.  E.  Gellert,  "proves  the  existence  of  a  phlogiston  in  the  animal  king 
dom"  (47},  Before  the  true  nature  of  combustion  was  understood,  it 
was  regarded  not  as  a  combination  of  oxygen  with  the  combustible  sub 
stance  but  as  the  escape  of  a  volatile  principle  called  "phlogiston,"  In 
1780  J.  G.  Gahn  found  that  the  "green  lead  ore"  of  Breisgau  is  a  natural 
lead  phosphate  and  thus  demonstrated  the  presence  of  phosphorus  in 
the  mineral  kingdom  (48,  49),  This  discovery  was  confirmed  by  M.  H, 
Klaproth  a  few  years  later  in  his  analysis  of  a  "green  crystalline  cerussite" 
from  the  Holy  Trinity  Mine  at  Zschopau  near  the  Erzgebirge  (50,  51). 
From  Klaproth's  description  of  this  mineral  it  was  probably  pyromorphite. 

After  mentioning  some  acids  found  in  only  one  of  the  three  natural 
realms,  the  Swedish  chemist  Torbern  Bergman  stated  that  "Other  acids 
are  common  to  all  the  kingdoms  of  nature,  as  the  phosphoric,  which  has 
been  falsely  assigned  to  the  animal  kingdom  alone,  but  which  has  been 
found,  though  rarely,  in  the  fossil,  and  in  great  plenty  in  the  vegetable 
kingdom.  ...  Of  all  the  acids,  that  of  phosphorus  is  the  scarcest,  and 
has  hitherto  been  found  with  a  spataceous  kind  of  lead  only"  (52).  In 


MORE  ON  THE  DISCOVERY  OF  PHOSPHORUS  135 

Bergman's  time  the  word  "fossil"  meant  mineral  or  anything  dug  from 
the  earth. 

Many  early  chemists  observed  that  when  ordinary  white  phosphorus 
was  exposed  to  light,  even  in  a  vacuum,  it  became  red.  Although  the 
great  Swedish  chemist  T.  T.  Berzelius  regarded  the  red  substance  as  a 

11TT 

modification  of  phosphorus,  others  believed  that  an  oxide  had  been 
formed  by  interaction  of  the  insufficiently  dried  phosphorus  with  water. 
Anton  von  Schrotter  isolated  the  red  substance,  made  a  thorough  study 


Johan  Gottschalk  Wallerius,  1709-1785. 

Swedish  chemist,  physician,  mineralo 
gist,  and  agriculturist.  T,  Bergman's 
predecessor  as  professor  of  chemistry, 
metallurgy,  and  pharmacy  at  Upsala. 
In  his  analyses  of  bone  and  other  animal 
substances  in  1760,  he  detected  the  cal 
cium  but  not  the  phosphorus 


Courtesy  Edgar  Fahs  Smith 
Memorial    Collection 


of  its  properties,  and  confirmed  Berzelius's  opinion.  Schrotter  found  that 
in  an  inert  atmosphere  phosphorus  can  be  transformed  from  one  allo- 
tropic  form  to  the  other  without  change  of  weight  (53). 

Since  the  red  modification  can  be  handled  much  more  safely  than 
white  phosphorus  this  discovery  has  been  extremely  beneficent  to 
workers  in  the  match  industry.  As  early  as  1851  von  Schrotter  prepared 
matches  with  it,  but  they  were  not  easily  ignited.  H.  Hochstatter  of 
Langen,  near  Frankfort-on-the  Main,  exhibited  successful  red  phos 
phorus  matches  at  the  London  Exhibition  of  1872  (54).  The  Hoch 
statter  matches,  according  to  von  Schrotter,  "can  be  struck  even  upon 
cloth,  they  bum  quietly,  .  .  .  almost  without  smoke  and  smell.  .  .  .  What 
is  still  more  important,  the  workmen  during  their  production  are  not 


136  DISCOVERY  OF  THE  ELEMENTS 

exposed  to  danger  of  any  kind  soever"  (54).  In  1856  von  Schrotter  was 
awarded  the  Montyon  Prize  which  had  been  established  by  the  Pans 
Academy  to  honor  those  who  have  made  notable  contributions  to 
hygienic  conditions  in  industry. 

Anton  Schrotter,  the  son  of  an  apothecary  at  Olmiitz,  Austria,  studied 
medicine,  chemistry,  and  physics,  and  in  1830  received  an  appointment 
in  the  Technical  Institute  in  Graz,  Austria.  In  1843  he  was  called  to 
the  Polytechnic  Institute  in  Vienna.  After  twenty-five  years  of  out 
standing  service  there  he  was  appointed  Director  of  the  Mint  (55).  His 
last  contribution  to  science  was  a  chapter  on  "Phosphorus  and  matches" 
in  Dr.  A.  W.  von  Hermann's  "Report  on  the  Development  of  Chemical 
Industry  During  the  Last  Decade,"  which  was  published  in  Brunswick 
in  1875-77  (55). 

For  further  details  concerning  the  history  of  the  match  industry  the 
reader  may  consult,  for  example,  the  series  of  articles  published  by  M.  F 
Crass,  Jr.,  in  volume  18  of  the  Journal  of  Chemical  Education  in  1941 
(28)  and  Professor  Laszlo  (Ladislaus)  von  Szathmary's  "History  of  the 
Match  up  to  the  End  of  the  Nineteenth  Century"  (56).  The  early 
history  of  the  manufacture  of  phosphorus  in  America  has  been  described 
in  the  Journal  of  Chemical  Education  in  an  interesting  article  by  William 
E.  Gibbs  and  Claude  K.  Deischer  (57). 

Gahn  was  a  man  of  broad  interests  who  "often  laid  aside  the  Philo 
sophical  Transactions  or  his  blow-pipe  to  read  aloud,  near  the  sewing- 
table  in  the  next  room,  now  a  poem  by  Kellgren,  Fianzen,  Fru  Lenngren, 
Leopold,  or  Voltaire,  now  a  comedy  by  Mohere  or  Holberg;  or  to  exhibit 
a  little  mechanical  or  optical  masterpiece;  or  to  study  the  instruments 
for  some  household  art  and  present  a  method  of  improving  them"  (44). 

During  the  preparations  for  his  daughter  Margareta's  wedding,  Gahn 
and  his  family  witnessed  a  most  unusual  manifestation  of  household 
chemistry.  Since  the  recipe  for  salting  ham  with  a  brine  containing 
sugar  and  saltpeter  had  been  lost,  Fru  Gahn  trusted  to  her  memory,  and 
made  the  mistake  of  adding  altogether  too  much  saltpeter  and  too  little 
water.  On  the  wedding  day,  when  the  ham  was  being  boiled  in  the  brine, 
the  terrified,  breathless  housekeeper  came  running  in  to  report  that  the 
ham  had  burst  into  flame  and  was  throwing  out  flashes  of  lightning,  and 
that  the  house  was  in  danger  of  burning  down.  The  ensuing  scene  was 
described  by  Gahn  himself  in  a  letter  written  to  Berzelius  on  September 
20,  1807:  "It  was  really  a  peculiar  and  pretty  sight:  first  there  rose,  over 
the  entire  surface  of  the  water  in  the  kettle,  bright,  flashing  sparks,  which 
silently  appeared  and  disappeared;  then  long  and  sometimes  brilliant  and 
violent  streams  of  flashes  were  thrown  in  all  directions  over  the  water" 
"After  the  kettle  had  been  removed  from  the  fire  and  left  to 


MORE  ON  THE  DISCOVERY  OF  PHOSPHORUS  137 

cool,"  said  Gahn,  "I  could  see  that  the  shining  particles  were  originally 
small  oil-like  drops,  several  of  which  I  quickly  caught,  and  picked  up,  and 
found  to  be  actually  phosphorus!"  (45). 

The  kind  assistance  of  Dr.  Max  Speter  of  Berlin,  who  graciously 
contributed  a  number  of  important  references  on  the  early  ^history  of 
phosphorus,  is  gratefully  acknowledged. 

LITERATURE  CITED 

( 1 )  PETERS,  HERMANN,  "Gesclnchte  des  Phosphors  nach  Leibniz  and  dessen  Brief - 

wechsel,"  Chem-Ztg.,  26,  1190-8  (Dec.  13,  1902). 

(2)  KUNCKEL,  J.,  "Vollstandiges  Laboratonum  Chymicum"  4th  edition  Rudigersche 

Buchhandlung,  Berlin,  1767,  pp   605-9. 
(5)     DAVIS,  T,  L.    "Kunckel  and  the  early  history  of  phosphorus,"  /.  Chem.  Educ., 

4,  1105-13  (Sept,  1927). 
(4}     LEIBNIZ,  G  W.,  "Geschichte  der  Erfindung  des  Phosphors,"  Crell's  Neues  chem. 

Archiv,  ls  213-18  (1784). 

(5)  "Oeuvres   Completes   de   Christian   Huygens,"  Vol    8,   Soc.   Hollandaise   des 

Sciences,  The  Hague,  1899,  pp.  217,  236,  238,  248-9,  251-2,  256-7,  267, 
ibid.,  Vol  10,  1905,  pp.  688-9,  696-7. 

(6)  "The  Works  of  the  Honourable  Robert  Boyle,"  Vol  4,  A.  Millar,  London,  1744, 

p    21 

(7)  BOYLE,  R.,  "A  phosphorus,"  Phil    Trans.  Abridgment,  5th  edition,  3,  353-4 

(1749);  Phil  Trans.,  17,  583-4  (Jan.,  1692). 

(8)  SPETER,  MAX,  "Zur  Geschichte  des  Urm-Phosphors :    Das  entdeckte  Phosphor 

Rezept  von  Boyle-Hanckwitz,"  Chem-Ztg.,  53,  1005-6  (Dec.  28,  1929). 

(9)  SMITH,  E  F.,  "Forgotten  chemists,"  J.  Chem.  Educ  ,  3,  39-40  (Jan.,  1926). 

(10)  HANCKWITZ,  A.  G.,  "Some  experiments  on  the  phosphorus  unnae  .  .  .  with 

several  observations  tending  to  explain  the  nature  of  that  wonderful  chemical 
production,"  Phil.  Trans.,  38,  58-70  (1733-4);  Phil  Trans,  Abridgment, 
ref.  (7),  9,  373-9  (1747);  Crell's  Neues  chem,  Archiv,  3,  6-14  (1785) 

(11)  "Mineralogische,  Ghymische,  und  Alchemistische  Brief e   von  reisenden  und 

anderen  Gelehrten  an  den  chemahgen  Chursachsischen  Bergrath  J.  F. 
Henkel,"  3  vols.,  Walthensche  Buchhandlung,  Dresden,  1794-95. 

(12)  BUGGE,  G.,  "Das  Buch  der  grossen  Chemiker,"  Vol.  1,  Verlag  Chemie,  Berlin, 

1929,  pp.  231-4.    Article  on  Marggraf  by  Max  Speter. 

(13)  MARGGRAF,  A.  S  ,  "Verschiedene  neue  Arten,  den  Harnphosphorus  leichter  zu 

verfertigen,  und  ihn  geschwind  aus  Phlogiston  und  emem  besondern  Harn- 
salze  zusammenzusetzen,"  Crell's  News  chem.  Archiv,  3,  300-3  (1785), 
No.  187  of  Ostwald's  Klassiker  der  exakten  Wissenschaften. 

(14)  SPETER,  MAX,  "Zur  Geschichte  des  Marggraf schen  Urm-Phosphors,"  Chem.- 

techn   Rundschau,  44,  1049-51  (Aug.  13,  1929) 

(15)  INGE,  J.,  "Ambrose  Godfrey  Hanckwitz,"  Pharm.  J ,  [1],  18,  126-30,  157-62, 

215-22  (Aug,  Sept,  Oct.,  1858) 

(16)  INGE,  J.,  "On  the  discovery  of  phosphorus,"  &id.,  [1],  13,  280-2  (Dec.,  1853). 

(17)  GORE,  G.,  "On  the  origin  and  progress  of  the  phosphorus  and  match  manu 

factures,"  Chem  News,  4,  16-18  (July  13,  1861). 

(18)  STEPHEN,  L   and  S.  LEE,  "Dictionary  of  National  Biography/'  Vol.  22,  Mac- 

millan  and  Co  ,  London,  1890?  pp  30-1.  Article  on  Godfrey  or  Godfrey- 
Hanckwitz 

(19)  "Nitrogen  and  phosphorus.    A  classic  of  science,"  ScL  News  Letter,  22,  102r-3 

(Aug.  13,  1932).   Reprint  of  Boyle s  "Aerial  Noctiluca,"  ref.  (6). 


138  DISCOVERY  OF  THE  ELEMENTS 

(20)  DERHAM,  W.,  "Philosophical  experiments  and  observations  of  the  late  eminent 

Dr.  Hobert  Hooke,  F.R  S.  .  .  .  and  other  eminent  Virtuoso's  in  his  time/3 
W.  and  J.  Innys,  London,  1726,  pp.  178-81. 

(21 )  LEWIS,  WILLIAM,  "The  Chemical  Works  of  Caspar  Neumann,  M  D./'  Johnston, 

Keith,  Linde,  etc.,  London,  1759,  p    582. 
(22}     PILCHER,  R.  B.,  "Boyle's  laboratory,"  Ambte,  2,  Plate  VII  (June,  1938} 

(23)  GUNTHER,  R    T.,  "Early  Science  in  Oxford/'  Vol    8,  printed  for  the  author, 

Oxford,  1931,  pp.  271-82.  Boyle's  "Shoit  memorial  of  some  observations 
made  upon  an  artificial  substance  that  shines  without  precedent  illustiation/' 
Sept.,  1677. 

(24)  MACQUER,  P  -J  ,  "Elements  of  the  Theory  and  Practice  of  Chymistry/'  2nd  ed,, 

Vol.  1,  A.  Millar  and  J.  Nourse  London,  1764,  pp   273-7. 

(25)  WEEKS,  M  E,,  "Max  Speter,  1883-1942,"  Isis,  34,  340-4  (Spring,  1943). 

(26)  TESTI,  GINO,  "Un  punto  oscuro  di  storia  della  chimica  da  investigare     L'opeia 

di  Raimondo  di  Sangro,"  La  CUmica  neW  Industria,  nell'  Agricoltura,  e 
nella  Biologia,  6,  412-13  (Oct.  31,  1930),  Archeion,  13^67-8  (1931) 

(27)  VON-  KLINCKOWSTROEM,  GAEL  GRAF,  "Raimondo  di  Sangro,"  ibid,  14,  490-1 

( 1932) 

(28)  CRASS,  M   F.,  JR.,  "A  history  of  the  match  industry/7  J.  Chem  Educ  ,  18,  116 

(Mar,  1941). 

(29)  WATTE,  A,   E.,   "The  Hermetic  and  Alchemical  Writings   of  Paracelsus  the 

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(30)  GTJNTHER,  R.  T.,  "Early  Science  in  Oxford/'  ref   (23),  Vol.  7,  pp  588-9. 

(31)  LEMERY,  N.,  "A  Course  of  Chymistry/'  2nd  English  ed.  from  the  5th  Fiench, 

Waltei  Kettilby,  London,  1686,  p   529, 

(32)  NOLLET,   M.   I/ABBE,    "Legons  de  Physique  Experiment  ale/'   vol.   4,   Fieres 

Guerin,  Paris,  1748,  pp    228-36. 

(33)  MACQUER,  P.-J.,  "Elements  of  the  Theory  and  Practice  of  Chymistry/'  2nd  ed., 

Vol.  1,  A.  Millar  and  J.  Nourse,  1764,  pp   261-79 

(34)  ALBINUS,  B  ,  Dissertafao  de  Phosphoro  Liquido  et  Sohdo/*  Frankfuit-on-the 

Oder,  1688. 

(35)  MARGGRAF,  A.  S,,  "Chymische  Schriften/*  revised  ed,3  Vol.  1,  Arnold  Wever, 

Berlin,  1768,  pp.  75-7,  104-5. 

(36)  FRIEND,  J.  N.,  "A  Textbook  of  Inorganic  Chemistry,"  Vol    6,  part  2,  Charles 

Griffin  and  Co.,  London,  1934,  pp  4-5     "Phosphorus"  by  E.  B,  R.  Pndeaux. 

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(38)  MEYER,  J.  K.  F.,  "Ueber  die  Phosphorsaure  in  dem  giunen  harzigten  Bestand- 

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(39)  LEWIS,  WILLIAM,  ref.  (21),  pp.  493-4. 

(40)  WALLERTUS,   J.    G.,    "Untersuchung   der  Erden   aus   Wasser,   Pflanzen,   und 

Thieren,  drittes  Stuck,  von  der  Erde  aus  Thieren,"  C fell's  Neues  chem. 
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(43)  NOBDENSKIOLD,  A.  E  ,  "C.  W.  Scheele.     Nachgelassene  Brief  e  und  Aufzeich- 

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(44)  TARTA,  HANS,  "Aminnelse-tal  ofver  Herr  Joh.  Gotti.  Gahn,"  P.  A.  Norstedt  and 

Sons,  Stockholm,  1832,  51  pp. 

(43)  .SODERBAUM,  H.  G.,  "Jac  Berzehus  Brev,"  part  9,  Almqvist  and  Wiksells 
Publishing  Co.,  Upsala,  19225  pp  18-19.  Letter  of  Gahn  to  Berzelius, 
Sept.  20,  1807. 


MORE  ON  THE  DISCOVERY   OF  PHOSPHORUS  139 

(46)  BOERHAAVE,  HERMAN,  "Siemens  de  Chymie,"  Vol.  1,  Chardon  fils,  Pans,  1754, 

pp.  Iviii-lix. 

(47)  GELLERT,  C.  E,,  "Metallurgy  Chemistry,"  T.  Becket,  London,  1776,  p    28 

(48)  BERGMAN,  TORBERN,  "Opuscula  physica  et  chemica,"  Vol.   2,  I.   G.   Muller, 
K  Lipsiae,  1792,  p   424;  "De  mmerarum  docimasia,"  Upsala,  1780 

(49)  "Encyclopedic  m6thodique,     Chimie  et  metallurgy  par  M.  Fourcroy,"  Vol    5, 

H    Agasse,  Pans,  1808,  p.  638. 

(50)  KOBELL,  FRANZ  VON,  "Geschichte  der  Mineralogie  von  1650-1860,"  J.  G.  Cotta, 

Munich,  1864,  pp.  5S&-7,  540,  609-10. 

(51)  KXAPROTH,  M.   H.,  "Ueber  die  Phosphorsaure  im  Zschopauer  grunen  Bley- 

spathe,"  Crell's  Beytrage  zu  den  Chem.  Ann ,  1  (part  2),  13-21  ( 1785). 

(52)  "Physical  and   Chemical  Essays   Translated  from  the   Original  Latin   of   Sir 

Torbern  Bergman,"  Vol.  3,  Mudie,  Farrbaixn,  and  J.  Evans,  London,  1791, 
pp.  261  and  281. 

(53)  SCHROTTER,  A.  VON,  "Neue  Modification  des  Phosphors/'  Ann ,   68,  247-53 

(1848),  J  prakt.  Chem.,  (1),  51,  155  (1850). 

(54)  SCHROTTER,  A.  VON,  "Phosphorus  and  matches,"  Chem.  News,  36,  208,  219-21 

(Nov.  9-16,  1877). 

(55)  KOHN,   MORITZ,   "The   discovery   of  red   phosphorus    (1847)    by  Anton   von 

Schrotter  (1802-1875),"  J.  Chem   Educ,,  21,  522  (Nov.,  1944) 

(56)  SZATHMARY,  LAszLO,  "A  Gyufa  Tortenete  a  XlX-ik  Szazad  Vegeig,"  A  Kis 

Akademia  Kiadasa,  Budapest,  1935,  127  pp  ,  Nouvelles  de  la  Chimie,  No 
23  (Nov,  1936);  SZATHMARY,  LADISLAUS  VON,  "Stephan  Romer,  der 
Fabrikant,  and  Johann  Innyi,  der  Ideeeur-Erfinder  des  gerauschlos  entflam- 
menden  Phosphor-Zundholzes  von  Anno  1836,"  Z  fur  das  gesamte  Schiess- 
und  Sprengstoffwesen,  31,  No.  10,  333^7;  No.  11,  368-72;  No.  12,  1-3 
(1936).  Translated  from  Hungarian  into  German  by  Max  Speter 

(57)  GIBBS,  W.  E.  and  C.  K.  DEISCHER,  "George  Rose-    A  pioneer  in  American 

phosphorus  manufacture  from  1870  to  1899,"  /.  Chem.  Educ.,  27,  269-73 
(May,  1950). 

(58)  WINDERLICH,   RUDOLF,    "Brennglaser   als   Hilfsmittel   chemischen   Forschens," 

Chymia,  2,  37-43  (1949). 


Andreas  Sigismund  Marggraf,  1709- 
1782.  German  chemist  who  distin 
guished  between  potash  and  soda,  real 
ized  that  clay  contains  the  peculiar 
oxide  now  known  as  alumina,  recog 
nized  magnesia,  isolated  zinc  from  cala- 
mine,  and  discovered  sugar  in  the  beet. 

From  Bugge's  "Das  Buch  der  grossen  Chemiker"1 


"Knowing  how  contented,  free  and  joyful  is  life  in 
the  realms  of  science,  one  fervently  wishes  that  many 
would  enter  their  portals."  (1). 


Some  eighteenth-century  metals 


Among  the  metals  isolated  in  the  eighteenth  century  may  be  men 
tioned  zinc,  cobalt,  nickel,  and  manganese,  the  last  three  of  which 
were  discovered  in  Sweden.  The  researches  of  Marggraf,  Georg 
Brandt,  Cronstedt,  and  Gahn  which  led  to  the  recognition  and 
isolation  of  these  elements  were  scientific  contributions  of  the 
first  rank,  and  the  personalities  of  these  great  men  are  well  worthy 
of  study  and  emulation.  Other  metals  of  this  period  will  be  dis 
cussed  in  later  chapters. 

ZINC 


liny  the  Elder  and  Dioscorides  o£  Anazarbus  mentioned  that 
zinc  compounds  were  used  for  healing  wounds  and  sore  eyes  (41,42).  In 
the  latter  part  of  the  thirteenth  century  A.D.,  Marco  Polo  described 
the  manufacture  of  zinc  oxide  in  Persia:  "Kubenan  is  a  large  town.  The 
people  worship  Mahonunet.  There  is  much  iron  and  steel  ,  .  .  They 
also  prepare  both  Tutia  (a  thing  very  good  for  the  eyes)  and  Spodium; 
and  I  will  tell  you  the  process.  They  have  a  vein  of  a  certain  earth 
which  has  the  required  quality,  and  this  they  put  into  a  great  flaming 
furnace,  whilst  over  the  furnace  there  is  an  iron  grating.  The  smoke  and 
moisture,  expelled  from  the  earth  of  which  I  speak,  adhere  to  the  iron 
grating,  and  thus  form  Tutia,  whilst  the  slag  that  is  left  after  burning  is 
the  Spodium'  (43). 

Brass.  Centuries  before  zinc  was  discovered  in  the  metallic  form, 
its  ores  were  used  for  making  brass. 

Strabo  of  Amasia,  Asia  Minor  (66  B.C.-24  A,D.}>  said  in  his  geog 
raphy  that  only  the  Cyprian  ore  contained  "the  cadmian  stone,  copper 
vitriol,  and  tatty,"  that  is  to  say,  the  constituents  from  which  brass  can 
be  made  (90).  He  also  mentioned  "a  stone  in  the  neighbourhood  of 
Andeira  which,  when  burned,  becomes  iron,  and  then,  when  heated  in 
a  furnace  with  a  certain  earth,  distils  mocksilver  [zinc];  and  this,  with 
the  addition  of  copper,  makes  the  mixture,  as  it  is  called,  which  by  some 
is  called  mountain-copper  [orichalcum,  or  brass]"  (91). 

The  Romans  manufactured  a  copper-zinc  alloy  which  they  called 
orichalcum  or  aurichalcum.  In  speaking  of  copper,  Pliny  the  Elder 

141 


142  DISCOVERY   OF   TfeE  ELEMENTS 

said  that  "The  ore  is  mined  as  already  related,  and  smelted.  The  metal 
is  prepared  also  from  a  coppery  mineral  called  cadmea.  ,  .  .  Cyprian 
copper  soon  became  very  cheap  when  better  kinds,  more  particular!} 
aurichalcum,  were  found  elsewhere  ..."  (92).  Of  the  Marian,  or 
Cordovan,  copper  he  said,  "It  is  only  surpassed  by  the  Livian  in  its 
power  of  alloying  with  cadmea,  and  sesterces  and  two-as  pieces  made 
from  it  are  so  fine  as  to  counterfeit  aurichalcum."  The  Latin  word 
cadmea  refers  both  to  zinc  ores  and  to  the  volatized  zinc  oxide  (Ofen- 
bruch,  or  furnace  calamine)  obtained  by  roasting  them  (47).  These 
ores  included  both  the  hydrous  silicate  (calamine)  and  the  carbonate 
( smiths  onite). 

William  Gowland  stated  in  1912  that  the  Romans  first  made  brass 
in  the  time  of  Augustus  (20  B.C.  to  14  A.D.)  (93).  They  made  it  by 
heating  a  mixture  of  powdered  calamine,  charcoal,  and  granules  of  copper, 
keeping  the  contents  of  the  crucible  below  the  melting  point  of  copper. 
After  the  zinc  vapor  had  reacted  with  the  copper,  the  temperature  was 
raised  to  melt  the  brass.  This  "calamine  brass"  was  manufactured  in 
Europe  as  late  as  the  nineteenth  century.  Although  James  Emerson 
patented  a  process  in  England  in  1781  for  the  manufacture  of  brass  from 
copper  and  zinc  metals,  conservative  English  metallurgists  long  preferred 
the  calamine  process  ( 93 ) . 

Metallic  Zinc.  Ancient  metallurgists  probably  lost  the  volatile  zinc 
metal  as  vapor  because  their  apparatus  was  not  designed  for  condensing 
it.  E.  O.  von  Lippmann,  a  great  authority  on  the  history  of  science, 
searched  the  writings  of  Aristotle,  Pliny,  and  Dioscorides  in  vain  for 
any  mention  of  it,  but  an  idol  containing  87  5  per  cent  of  that  metal 
was  found  in  a  prehistoric  Dacian  ruin  at  Dordosch,  Transylvania  (2). 

According  to  the  Rasarnaua,  which  was  published  in  India  in  the 
thirteenth  century  A.D.,  metallic  zinc  was  prepared  by  reducing  calamine 
in  a  closed  crucible  with  organic  substances  such  as  lac  or  wool  (94). 
P.  C,  Ray  stated  that  the  Hindu  king,  Madanapala,  recognized  zinc  as 
a  metal  as  early  as  1374  (3),  and  it  is, probable  that  the  art  of  smelting  the 
ores  originated  in  India  and  was  carried  first  to  China. 

A  Chinese  book  entitled  "Tien  kong  kai  ou"  printed  in  1637  describes 
the  metallurgy  and  uses  of  this  metal  (2,  44).  As  early  as  the  sixteenth 
century,  Europe  was  importing  zinc  from  China,  where  the  large-scale 
production  of  it  probably  originated  (44,95).  In  his  extended  researches 
on  the  history  of  zinc,  W.  Hommel  analyzed  a  specimen  of  this  metal 
which  had  once  formed  part  of  the  cargo  of  the  East  India  Company^ 
ship  Gotheborg  which  sank  near  Gothenburg,  Sweden,  in  1745.  He 
found  it  to  be  very  pure  (44).  Although  small  amounts  of  zinc  for 
medicinal  purposes  were  prepared  in  India  in  the  thirteenth  and  four- 


Z.  angettx.  diem..,  1912 

Production  of  Zinc  in  China   as  pictured  in  the  Chinese  technical  lexicon 

"Tien  kong  kai  ou/? 


144  DISCOVERY  OF  THE  ELEMENTS 

teenth  centuries,  the  technical  production  of  it  originated  in  China  m 
the  sixteenth  century.  Hornmel  quoted  from  the  1637  edition  of  the 
"Tien  kong  kai  ou"  the  following  description  of  the  process:  "One 
strongly  compresses  the  ore  [Lu-kan-shi,  or  calamine]  in  clay  crucibles 
having  covers  well  luted  with  loam.  The  crucibles  are  piled  up  in  a 
pyramid  with  lump  coal  between  them,  and,  after  being  brought  to 
redness,  are  cooled  and  broken.  The  metal  is  found  in  the  center  in 
the  form  of  a  round  regulus"  (44). 

Johann  Beckmarin,  in  his  "History  of  Inventions,"  quoted  the  fol 
lowing  passage  from  the  1616  Strasburg  folio  edition  of  the  works  of 
Paracelsus  ( 1493P-1541 ) :  "There  is  another  metal,  zinc,  which  is  in 
general  unknown.  It  is  a  distinct  metal  of  a  different  origin,  though 
adulterated  with  many  other  metals.  It  can  be  melted,  for  it  consist? 
of  three  fluid  principles,  but  it  is  not  malleable.  In  its  colour  it  is  unlike 
all  others,  and  does  not  grow  in  the  same  manner;  but  with  its  ultima 
materia  I  am  as  yet  unacquainted,  for  it  is  almost  as  strange  in  its 
properties  as  argentum  vivum  [quicksilver].  It  admits  of  no  mixture, 
will  not  bear  the  fabrications  of  othei  metals,  but  keeps  itself  entirely 
to  itself"  (47).  A  similar  passage  appears  in  the  "Book  of  Minerals," 
which  forms  part  of  the  Latin  folio  edition  of  Paracelsus's  works  pub 
lished  m  Geneva  in  1658  (96). 

In  the  seventeenth  century,  miners  believed  that  base  metals  gradu 
ally  develop  in  the  mine  into  the  more  perfect  ones  such  as  silver  and 
gold.  J.  R.  Glauber  said  that  "when  the  miners  sometimes  dig  up  an 
untimely  ore,  such  as  bismuth,  cobalt,  or  zinc,  and  test  it  for  silver  with 
out  finding  any,  they  say?  we  have  come  too  soon  .  .  ."  (97).  Glauber, 
however,  did  not  share  the  general  belief  in  the  close  relationship  be 
tween  the  planets  and  the  metals.  "For,"  said  he,  "if  each  planet  gener 
ated  its  special  metal,  it  would  also  undoubtedly  choose  a  special 
place  and  would  not  allow  another  to  come  into  its  nest  and  interfere 
with  its  intention.  And  if  we  nevertheless  maintain  that  each  planet 
gives  biith  to  its  own  metal,  to  which  star  should  one  assign  bismuth, 
cobalt,  antimony,  and  zinc?"  (97). 

Geoffroy  the  Elder  (1672-1731)  described  zinc  as  "a  Metallick 
sulphureous  heavy  Substance  resembling  Lead  in  Colour,  fusible  and 
ductile  to  a  certain  Degree,  being  very  hard  to  break,  inflammable,  and 
volatile.  It  seems  to  have  been  quite  unknown  to  the  Antients,  and  even 
the  Moderns  knew  very  little  about  its  Nature  or  Origin  till  M.  Stahl, 
now  First  Physician  to  his  Prussian  Majesty,  explained  it  in  his  Dissertation 
De  Metallurgia.  It  is  extracted  from  the  Lead  Oar  of  the  Mines  of  Gos- 
selaar  [Goslar].  .  .  .  Three  substances  are  separated  from  it:  Lead,  Zinch, 
and  a  Kind  of  Cadmia  Fornacea,  which  being  melted  with  Copper,  makes 


SOME  EIGHTEENTH-CENTURY   METALS  145 

a  Prince's  or  Bath  Metal.  ,  .  ,  The  Pewterers  use  Zinch  in  whitening  and 
purifying  Tin  .  .  ."  (98). 

"The  Modern  Cadmia,  Cadmia  Fornacum  of  Agricola,  Tutia  of  the 
shops,"  continued  Geoffrey,  "is  a  Recrement  of  Calamin,  melted  with 
Copper,  and  not  of  Copper  alone,  as  was  that  of  the  Antients.  The 
official  Tutty  theiefore  may  be  defined  as  a  Sublimation  of  Calamin 
from  melting  Copper  to  the  upper  Part  or  Roof  of  the  Furnace,  where  it 
concretes  round  Iron  Rods  placed  there,  into  a  solid  Crust,  which  is 
afterwards  beat  off  into  Pieces,  like  the  Bark  of  Trees,  of  a  yellowish 
Colour,  smooth  on  the  inside  and  sonorous;  of  a  bluish  Ash  Colour  on 
the  outside,  and  powdered  as  it  were  with  very  small  Grains  of  the 

same  Substance Tutty  is  reckoned  among  the  principal  Ophthalmick 

Medicines.  .  .  ,  The  Pompholyx  of  our  Shops,  Nihil  Album  of  some 
Authors,  is  a  fine  white  Flower,  or  Soot,  which  sticks  to  the  Arch  of  the 
Furnaces  and  Covers  of  the  Crucibles  in  which  Calamin  and  Copper 
are  melted  together  .  ,  ."(98). 

A  hundred  years  before  zinc  was  smelted  in  Europe,  it  was  being 
sold  there  by  Portuguese  traders  who  brought  it  from  the  Orient  (4}. 
G.  Agricola  mentioned  the  formation  of  "zincum"  in  the  furnaces  in 
Silesia  (31).  Small  amounts  of  metallic  zinc  were  obtained  as  a  by 
product  of  the  lead  industry  at  Goslar,  Prussia,  and  G.  E.  Lohneyss  de 
scribed  the  process  as  follows:  "The  metal  zinc  or  counterfeht  is  formed 
under  the  smelting  furnaces  and  in  the  crevices  of  the  wall  where  the 
bricks  are  not  well  plastered  When  the  wall  is  scraped,  the  metal  falls 
down  into  a  trough  placed  to  receive  it.  The  metal  is  not  much  valued, 
and  the  workmen  collect  it  only  when  they  are  promised  Trinkgeld" 

(3,18,38). 

Caspar  Neumann  (1683-1737)  gave  the  following  first-hand  descrip 
tion  of  die  Goslar  zinc  works:  "The  greatest  quantities  of  Zinc  come  from 
the  East  Indies,  in  large  oblong  pieces;  and  from  Goslar,  commonly  in 
round  cakes  or  loaves.  Of  the  origin  of  the  East-India  Zinc  we  have  no 
certain  account:  The  Goslarian  is  extracted  from  the  Lead-  and  Silver-ores 
of  Rammelsberg  by  a  particular  contrivance  in  the  structure  of  the 
furnace.  The  Zinc,  naturally  contained  m  the  ore,  separates  during  the 
fusion  from  the  other  metallic  matters,  being  elevated  by  the  heat  in  form 
of  fume,  which  passes  into  a  reservoir  made  for  that  purpose  in  the  front 
wall,  over  die  gutter  by  which  the  Lead  runs  off.  The  reservoir  for  the 
Zinc  is  inclosed,  on  the  inside,  by  a  large  flat  stone,  only  some  chinks  being 
left  for  the  fumes  to  enter;  and  on  the  outside,  by  another  stone,  which 
is  closely  luted,  and  frequently  sprinkled  during  the  process  with  cold 
water,  to  cool  and  condense  the  fumes.  Each  smelting  lasts  twenty  hours, 
beginning  at  ten  in  the  forenoon  and  ending  at  six  next  morning.  When 


146  DISCOVERY  OF  THE  ELEMENTS 

the  fusion  of  the  ore  is  completed,  the  workman  dextrously  strikes  the 
outer  stone  of  the  reservoir  with  an  Iron  rod,  so  as  to  loosen  some  of  the 
luting  at  the  bottom;  upon  which  the  Zinc,  collected  during  the  process, 
runs  out  like  Quicksilver.  He  continues  to  tap  till  nothing  more  will 
run;  then  melts  the  Zinc  again  in  an  iron  pot,  and  casts  it  into  hemi 
spherical  masses,  I  have  several  times  been  at  this  work,  and  kept  at  it 
two  days  and  a  night  together  without  leaving  the  furnace. 

"Though  a  part  of  the  Zinc  is  thus  obtained  in  its  metallic  f  oim,  a  part 
is  also  dissipated,  and  a  veiy  considerable  one  adheres  to  the  sides  of 
the  furnace  in  the  form  of  a  calx,  .  .  .  The  produce  of  Zinc  is  extremely 
variable.  ...  At  Goslar,  when  the  due  precautions  happen  to  be 
neglected,  there  is  not  so  much  Zinc  detained  as  to  be  worth  collect 
ing  ..  :  (33). 

Johann  Andreas  Cramer  of  Blankenburg  (1710-1777),  in  his  "Ele 
ments  of  the  Art  of  Assaying  Metals/'  which  was  first  published  in 
Leyden  in.  1737,  wrote:  "Zinc  is  called  in  German  Contrafait  Spiauter; 
whether  it  is  or  ever  was  found  native,  in  the  same  Form  mentioned, 
is  a  Secret  to  me;  nor  is  there  any  known  kind  of  Ore,  out  of  which 
this  semi-Metal  may  be  melted.  .  .  .  Therefore,  all  the  Zink  that  is 
prepared  in  Germany,  especially  at  Goslar,  is  obtained  by  sublimation,  not 
by  Eliquation,  and  not  got  out  of  any  singular  Ore,  but  out  of  such  an 
intricate  and  confused  Mixture  of  different  Ores  that  several  other  Metals 
and  semi-Metals  may  be  separated  at  the  same  Time  from  it.  Iron,  Lead, 
and  Copper  are  also  contained  in  it  in  great  Plenty;  and  are  almost  all 
involved  in  Sulphur  and  Arsemck,  There  are  no  peculiar  Sublimations 
made  for  the  extracting  of  Zink,  but,  by  a  Sort  of  secondary  Operation, 
it  is  collected  during  the  Ehquation  of  the  other  Metals,  especially  of 
Lead.  .  .  . 

"However/*  continued  Cramer,  "there  are  besides  the  Matrixs  [sic] 
of  Zink  hitherto  mentioned,  that  are  found  at  Goslar,  some  others  which 
may  be  called  Zink  Ores,  To  this  class  belongs  especially  the  Lapis 
Calaminaris,  or  Calamine,  in  German  Galmey,  and  also  native  Cadmia, 
to  distinguish  it  from  that  which  is  called  Furnace-cadmia.  .  .  .  You 
can  never,  by  the  only  Force  of  Fire,  or  by  the  help  of  the  common 
reducing  Fluxes,  produce  any  Zink  out  of  this  Stone.  However,  the 
Agreeableness  of  the  Flowers  of  the  said  Stone  with  those  of  Zink,  the 
changing  of  the  red  Colour  of  Copper  into  the  yellow  gold  Colour  ( brass ) , 
which  alteration  is  effected  both  by  the  Calamine  and  by  Zink;  and 
finally,  the  Production  of  Zink  itself  out  of  the  Lapis  Calaminaris,  to  be 
obtained  by  several  manual  Operations,  require  that  we  should  class  it 
among  Zink-Ores.  .  .  .  Zink  is  confounded  with  Bismuth  by  several 
Authors.  .  .  . 


SOME  EIGHTEENTH-CENTURY  METALS  147 

"The  Dutch  bring  to  Europe  in  their  East  India  Ships,"  said  Cramer, 
'a  great  Quantity  of  Zink.,  which  is  a  little  more  blue  than  the  German 
Zink,  and  in  every  Respect  more  tenacious.  But  we  know  nothing  cer 
tain  either  of  the  Country  where  the  Ore  that  contains  this  Zink  is 
digged  out  or  ...  of  the  Manner  in  which  Zink  is  obtained  out  of  it. 
For  they  say  no  European  is  granted  the  Liberty  of  entering  into  those 
Countries"  (51,  99). 

Johann  Kunckel  and  Geoig  Ernst  Stall  believed  that  the  ore  calamine 
contained  a  metal  that  alloys  with  copper  to  form  brass,  and  even  as 
late  as  1735,  the  Swedish  chemist  Georg  Brandt  thought  that  calamine 
could  not  be  reduced  to  a  metal  except  in  presence  of  copper  (2,  19). 
During  the  years  between  1768  and  1781,  Richard  Watson,  Bishop  of 
Llandaff,  published  his  famous  chemical  essays  (45).  In  the  one  on  zinc, 
he  quoted  the  following  passage  from  page  295  of  the  French  transla 
tion  of  J.  F.  HenckeTs  (or  Henkel's)  "Pyritologia":  "One  makes,  for 
example,  with  the  calamine,  not  only  iron  (in  small  amounts,  to  be  sure), 
but  also  a  very  large  quantity  of  zinc,  which  one  obtains  not  only  on 
presenting  to  it  the  substance  with  which  it  can  incorporate  itself  (that 
is  to  say,  copper,  which  is  its  lodestone),  but  also  this  half -metal  shows 
itself  simply  on  addition  of  a  fatty  substance  which  metallizes;  it  is  only 
necessary  to  avoid  letting  this  phoenix  be  reduced  to  ash,  to  keep  it  from 
burning,  and  to  observe  the  time  and  circumstances"  (46)  Henckel 
prepared  metallic  zinc  by  reduction  of  calamine,  but  kept  the  process 
secret  (29,  47).  As  the  shining  metal  came  forth  from  the  hard,  luster- 
less  ore,  he  was  reminded  of  the  Egyptian  symbol  of  immortality,  the 
phoenix,  a  fabulous  bird  which  rose  to  new  life  from  its  ashes, 

In  the  introduction  to  his  German  translation  of  P.  M.  de  Respour  s 
"Special  Experiments  on  the  Mineral  Spirit,"  Henckel  mentioned  in  1743 
that  "In  our  smelting  furnaces  at  Freyberg  we  have  obtained  the  essence 
of  zinc  [zinckische  Wesen]  in  power  but  not  in  form"  (48).  He  believed 
that  their  failure  to  obtain  "corporal"  [metallic]  zinc  must  have  been  due 
to  the  complex  nature  of  their  ore,  to  the  construction  of  their  furnaces, 
and  to  the  long- continued  heating,  which  made  it  "impossible  for  the 
phoenix,  even  when  resurrected  from  its  ash,  to  withstand  the  fire"  (48). 

"Nevertheless,"  said  Henckel,  "zinc  is  a  metal  with  regard  to  its 
consistency,  luster,  specific  gravity,  tenacity,  and  mercurial  fluidity  in 
the  fire,  but  also  not  a  metal  with  respect  to  its  flammability  and  com 
plete  combustibility,  wherein  it  is  entirely  different  from  all  other  metals" 
(48). 

The  Flemish  metallurgist  P.  M.  de  Respour  published  the  first  edi 
tion  of  his  "Special  Experiments  on  the  Mineral  Spirit"  in  1668,  when  he 
was  twenty-four  years  old.  He  prepared  a  minute  amount  of  metallic 


148  DISCOVERY   OF   THE   ELEMENTS 

zinc  by  gently  heating  a  mixture  of  zinc  oxide  and  fat  on  a  sandbath  for 
six  or  seven  days.  When  he  subsequently  distilled  this  mixture,  he  found 
in  the  retort  only  a  little  gray,  fuming  deposit  in  which  he  was  unable 
to  distinguish  any  metallic  particles.  When  he  rubbed  it  with  mercury, 
however,  and  distilled  off  the  latter,  he  obtained  a  little  metallic  zinc 

(48). 

Bishop  Watson  stated  that,  "though  Henckel  was  the  first,  Dr.  Isaac 
Lawson  was,  probably,  the  second  person  in  Europe  who  procured  zinc 
from  calamine,  .  .  .  Our  English  waters  .  .  speak  in  high  terms  of 
Lawson  .  .  ."  (46).  Since  the  Bishop  prefaces  his  description  of  the 
metal  with  the  words  "If  the  reader  has  never  seen  a  piece  of  zinc,"  it 
must  have  been  a  rarity  even  in  the  second  half  of  the  eighteenth  cen 
tury  (46). 

When  Lawson  observed  that  the  flowers  of  lapis  calaminaris  weie 
the  same  as  those  of  zinc  and  that  they  had  the  same  effect  on  copper, 
he  worked  tirelessly  until  he  found  a  method  of  separating  the  zinc  from 
this  mineral  He  never  realized  any  profit,  however,  from  this  dis 
covery  (46). 

While  in  Leyden,  Dr.  Lawson  belonged  to  a  scientific  club  presided 
over  by  the  great  Swedish  botanist  Carl  von  Linne,  and  became  so  en 
grossed  in  making  mmeralogical  analyses  that  he  gave  up  attending 
lectures.  Another  of  Lawson's  Leyden  contemporaries  who  held  him  in 
high  esteem  was  Dr.  Herman  Boerhaave  (49,  50). 

Johann  Andreas  Cramer  assisted  Dr.  Lawson  for  several  years  m 
his  chemical  experiments  in  Leyden.  In  the  preface  to  the  second  English 
edition  of  Cramer  s  "Elements  of  the  Art  of  Assaying  Metals,"  there  is 
a  fine  tribute  to  Dr.  Lawson,  who  "had  resided  much  longer  at  Leyden 
than  those  foreigners  usually  do  who  go  there  to  qualify  themselves  for 
the  Practice  of  Physick.  He  then  employed  himself  in  the  Cultivation 
of  those  arts  which  he  had  there  been  taught;  particularly  of  Chemistry, 
and  was  highly  esteemed  for  his  Skill  therein,  and  lived  in  great  Intimacy 
with  Boerhaave  .  .  «  and  with  several  other  Men  of  great  Learning,  who 
resided  in  that  University  .  .  .  as  also  with  Linnaeus.  .  .  .  Doctor  Lawson 
afterwards  served  as  Physician  to  the  British  Army  in  Flanders,  where, 
by  his  Death,  in  the  year  1745,  the  World  was  deprived  of  the  Advantage 
of  many  useful  Discoveries.  To  him  we  owe  several  of  the  Observations 
contained  in  this  Work.  .  ."  (51). 

In  a  great  research  "On  the  method  of  extracting  zinc  from  its  true 
mineral,  calamine.,"  A.  S,  Marggraf  in  1746  reduced  calamine  from  Poland, 
England,  Breslau,  and  Hungary  with  carbon  in  closed  retorts,  and  obtained 
metallic  zinc  from  all  of  them  (2,  19,  53).  He  found  the  ore  from 
Holywell  to  be  especially  rich  in  it.  He  stated  that  both  J.  H.  Pott  and 


SOME  EIGHTEENTH-CENTURY   METALS 


149 


J,  F,  Henckel  had  known  how  to  prepare  this  metal  and  keep  it  from 

burning. 

Marggraf  also  showed  that  the  lead  ores  of  Rammelsberg  contained 
zinc  and  that  zinc  can  be  prepared  from  blende,  or  sphalerite  ( 53 ) .  "Who 
would  think,"  said  he,  "that  this  furnace  calamine  [in  Saxony]  is  derived 


Courtesy  Virginia  Bartow 


Richard    Watson,    Bishop    of    Llandaff,    1737-1816. 

Professor  of  chemistry,  and  later  professor  of  divinity, 
at  Cambridge.  Between  1768  and  1781  he  published 
a  collection  of  chemical  essays  on  water,  air,  coal,  lead, 
zinc,  salt,  saltpeter,  and  other  common  substances.  He 
gave  an  excellent  account  of  the  early  history  of  zinc 


from  blende  and  that  this  blende  contains  the  zinc  earth,  for  I  know  of  no 
one  who  ever  thought  of  it  except  the  aforementioned  Herr  Professor 
Pott,  who  mentioned  on  page  119  of  his  treatise  on  pseudo-galena  that 
pulverized  blende,  melted  with  carbon  and  copper,  did  not,  to  be  sure, 


150  DISCOVERY  OF  THE  ELEMENTS 

entirely  convert  the  copper  to  brass,  yet  made  it  rather  yellow,  and 
therefore  correctly  concluded  that  it  must  contain  an  earth  related  to 
calamine.  Still  less  has  anyone,  so  far  as  I  know,  ever  yet  made  known 
the  process  of  actually  preparing  zinc  from  this  mineral,  which,  however, 
I  hope  to  make  clear  from  the  following  experiment"  (53). 

Marggraf  was  probably  unaware  that  in  1742  Anton  von  Svab,  a  step 
brother  of  Emanuel  Swedenborg,  had  distilled  zinc  from  calamine  at 
Vestervik,  Dalecarlia,  and  that,  two  years  later,  he  had  even  prepared 
it  from  blende  (IS).  Since  the  vapors  rose  to  the  top  of  the  alembic 
before  passing  into  the  receiver,  this  process  was  called  distillation  per 
ascensum.  In  the  fall  of  1752  Svab  and  A.  F.  Cronstedt  developed  at 
government  expense  the  use  of  Swedish  zinc  ores  in  the  manufacture  of 
brass,  to  avoid  the  necessity  of  importing  calamine.  They  installed 
equipment  near  Skisshyttan  for  the  washing,  slow  oxidation,  decomposi 
tion,  and  calcination  of  the  ore  and  for  distillation  of  the  zinc.  Svab 
showed  that  blende  can  be  reduced  even  in  the  absence  of  copper  (52), 
In  1755  Cronstedt's  share  in  the  work  was  taken  over  by  Sven  Rinman 
(32,  46,  47).  Rinman  so  improved  the  metallurgical  process  that  zinc 
could  be  smelted  not  merely  in  the  form  of  grains  or  powder,  which 
required  subsequent  melting  and  consequent  loss  of  metal,  but  also  in 
fluid  form  directly  from  the  ore  (SI). 

Some  Famous  American  Zinc  Mines.  In  1810  Dr.  Archibald  Bruce 
analyzed  a  new  orange-red  mineral  from  Fianklin  Furnace,  Sussex 
County,  New  Jersey,  and  found  it  to  be  zinc  oxide  containing  a  little 
manganese.  This  mineral  is  now  known  as  zincite  (100, 101,  102). 

Archibald  Bruce  was  born  and  educated  in  New  York  City.  His 
father,  a  British  army  surgeon  stationed  in  New  York,  always  declared 
that  his  son  should  never  be  educated  for  the  medical'profession,  •  The 
boy's  natural  inclination  led  him,  however,  to  study  medicine  and 
allied  sciences  secretly  while  enrolled  in  the  arts  course  in  Columbia 
College.  His  favorite  recreation  was  the  collection  and  study  of  minerals. 
After  studying  abroad  for  several  years  he  received  his  degree  of  doctor 
of  medicine  from  the  University  of  Edinburgh  in  1800.  During  a  two- 
year  tour  of  France,  Switzerland,  and  Italy,  he  exchanged  American 
minerals  for  European  specimens  and  thus  built  up  a  valuable  collection. 
After  his  return  to  New  York  in  1803  he  engaged  in  a  successful  practice 
of  medicine  (103).  He  also  served  as  professor  of  materia  medica  and 
mineralogy  in  the  Medical  Institution  of  the  State  of  New  York  and 
Queen's  College,  New  Jersey.  Among  his  friends  and  correspondents 
were  Mr.  Greville  of  Paddington  Green,  near  London,  Count  J.-L.  Bour- 
non,  Sir  Joseph  Banks,  and  the  Abb6  R.-J.  Hairy.  Dr.  Bruce  died  in  New 
York  in  1818  at  the  age  of  forty-one  years. 


SOME  EIGHTEENTH-CENTURY   METALS  151 

Among  the  remarkable  zinc  minerals  at  Franklin  Furnace  Dr.  Bruce 
also  found  another  new  one  which  was  black.  When  P.  Berthier  analyzed 
a  specimen  of  it,  he  found  it  to  be  composed  of  the  oxides  of  iron,  manga 
nese,  and  zinc.  He  gave  it  the  name  franklinite  "derived  from  Franklin,  in 
order  to  remind  us  that  it  was  found,  for  the  first  time,  in  a  place  to  which 
the  Americans  have  given  the  name  of  a  great  man,  whose  memory  is 
venerated  equally  in  Europe  as  in  the  new  world  by  all  the  friends  of 
science  and  humanity"  (101). 

A  third  remarkable  and  unusual  zinc  mineral  in  the  Franklin  ore 
body  is  willemite,  the  fluorescent  zinc  orthosilicate  which  was  first 
characterized  in  1829  by  Armand  Levy,  who  named  it  for  Willem  I  of 
the  Netherlands  (102). 

In  about  1830  an  unsuccessful  attempt  was  made  to  determine  the 
nature  of  a  peculiar  ore  from  the  Saucon  Valley  near  Bethlehem,  Pennsyl 
vania,  Mr.  W.  T.  Roepper,  who  afterward  became  the  first  professor  of 
mineralogy  at  Lehigh  University,  identified  it  as  calamine,  zinc  hydro- 
silicate,  and  produced  brass  by  smelting  it  with  native  copper  (110). 
The  history  of  early  zinc  works  in  the  Lehigh  Valley  has  been  ably 
presented  in  the  Journal  of  Chemical  Education  by  R.  D  Billinger  (110). 

When  Henry  R,  Schoolcraft  visited  the  lead  mines  of  Missouri  in 
about  1819,  he  noticed  that  the  zinc  sulfide  ore  sphalerite  was  also 
abundant  (111).  Even  in  the  early  nineteenth  century,  the  value  of 
sphalerite  was  not  appreciated.  In  Henry  R.  Schoolcraft's  report  on 
the  lead  mines  of  Missouri,  which  was  published  in  the  American  Journal 
of  Science  for  1821,  appears  the  statement:  "Zinc  is  abundant,  but  as 
the  ore  is  the  sulphuret,  it  is  not  very  valuable.  It  is  not  mentioned  that 
the  calamine,  which  is  the  useful  ore  of  zinc,  has  been  found"  (54}. 

Zinc  in  Plant  and  Animal  Nutrition.  In  1854  A.  Braun  discovered  the 
presence  of  zinc  in  plants  and  in  1869  J.  Raulin  proved  that  it  is  essen 
tial  for  the  growth  of  Aspergillus  (153,  154).  Its  important  role  in  the 
nutrition  of  many  plants  and  animals  has  been  demonstrated  repeatedly 
(104.,  105).  When  some  pecan  trees  growing  on  a  copper-deficient  soil 
were  treated  with  a  copper  solution,  the  only  trees  which  responded  fav 
orably  were  those  treated  with  a  solution  which  had  been  stirred  up  in  a 
galvanized  bucket  and  therefore  contained  zinc  unintentionally  (106). 
Zinc  solutions  are  now  used  in  the  treatment  of  pecan  rosette  and  other 
zinc- deficiency  diseases  of  fruit  trees  and  nut-bearing  trees  in  the  western 
states  (112). 

L,  B.  Mendel  and  H.  C.  Bradley  found  in  1905  that  the  snail  syco- 
typus  contains  zinc  in  the  liver  and  in  the  oxygen-carrying  protein  of  the 
blood,  hemosycotypin.  The  three  respiratory  proteins,  hemoglobin  of 
the  vertebrates,  hemocyanin  of  the  octopus,  and  hemosycotypin  of  the 


152  DISCOVERY  OF'  THE  ELEMENTS 

snail,  aie  thus  analogous.    Their  oxygen-carrying  metals  aie  respectively 
iron,  copper,  and  zinc  (107,  IIS). 

Because  of  the  importance  of  zinc  in  nutrition,  sensitive  methods 
have  been  devised  for  determining  it  in  plant  and  animal  materials,  soils, 
and  natural  waters  The  polarographic  method  has  been  used  with 
success  (108,  109). 


SOME  SWEDISH  METALS 

In  the  eighteenth  century  Sweden  outstripped  all  other  countries  in 
the  discovery  of  new  elements,  It  is  blessed  with  a  rich  supply  of  rare 
ores  and,  moreover,  it  had  a  long  succession  of  brilliant  chemists  and 
mineralogists  whose  greatest  delight  was  to  investigate  these  curious 
minerals.  In  the  century  following  the  accidental  discovery  of  phos 
phorus,  three  new  metals,  cobalt,  nickel,  and  manganese,  were  dis 
covered  by  Swedish  chemists. 


COBALT 

"Thus  with  Hermetic  art  the  Adept  combines 
The  Royal  acid  with  cobaltic  mines; 
Marks  with  quick  pen,  in  lines  unseen  portrayed, 
The  blushing  mead,  green  dell,  and  dusky  glade; 
Shades  with  pellucid  clouds  the  tintless  field, 
And  all  the  future  Group  exists  conceal'd; 
Till  waked  by  fire  the  dawning  tablet  glows, 
Green  springs  the  herb,  the  purple  -floret  blows, 
Hills,  vales,  and  woods  in  bright  succession  rise, 
And  all  the  living  landscape  charms  the  eyes"  "(62). 

Analyses  of  blue  glass  made  by  the  ancients  show  that  the  earliest 
specimens  were  colored  sometimes  with  cobalt  but  much  more  often 
with  copper  (64,  65,  66).  In  the  tomb  of  Tut-ankh-Amen  were  many 
specimens  of  dark  blue  glass,  only  one  of  which  was  found  to  contain 
cobalt  (67).  Archaeologists  from  the  University  of  Pennsylvania  dis 
covered  in  Nippur,  Mesopotamia,  an  authentic  specimen  of  artificial 
lapis  lazuli  dating  from  about  1400  B.C  and  sent  a  sample  of  it  to  Pro 
fessor  Neumann  of  the  Higher  Technical  School  of  Breslau  for  analysis. 
He  found  that  this  glass  contains  a  remarkably  high  cobalt  content, 
namely  about  0.93  per  cent  of  cobaltous  oxide.  Although  Neumann  and 
his  collaborators  had  analyzed  many  antique  glasses  dating  from  1500  B.C. 
to  800  A.D.  this  was  the  first  one  in  which  they  found  cobalt  (114).  R. 
belieyed  thaf  when  the  Persian  ceramist  Abulqasrrn  wrote 


SOME  EIGHTEENTH-CENTURY   METAJLS  153 

In  his  "Book  of  Gems  and  Perfumes"  in  1301  A.D.  that  one  takes  for 
coloring  the  glaze  "for  the  Sulaimani  blue  ...  for  every  forty  parts  of 
glass  frit  one  part  of  lagward  [lapis  lazuli,  or  ultramarine],"  he  must 
have  been  speaking  of  cobalt  ores;  true  lapis  lazuli  is  useless  for  this 
purpose  (115,  116). 

Paracelsus,  in  his  "Book  of  Minerals,"  which  forms  part  of  the  1658 
Latin  folio  edition  of  his  works,  gave  only  a  vague  description  of  cobalt 
(7),  The  unknown  author  of  the  writings  attributed  to  "Basil  Valentine" 
stated  in  his  treatise  "On  the  great  stone  of  the  ancient  philosophers" 
that  "Among  the  minerals  are  included  all  metals,  ores,  marcasite,  cobalt 
(Kobold),  talc,  zinc,  shining  pyrites,  and  stones"  (63).  P.-E.-M.  Berthe- 
lot  thought,  however,  that  metallic  cobalt  must  have  been  prepared  be 
fore  the  thirteenth  century,  for  the  alchemists  understood  how  to  roast 
and  reduce  ores,  They  did  not,  however,  know  how  to  refine  the  metals 
and  distinguish  between  them  (7). 

Near  the  end  of  the  fifteenth  century,  a  troublesome  and  supposedly 
worthless  mineral,  "cobalt,"  was  found  in  large  quantity  in  the  mines  on 
the  borders  of  Saxony  and  Bohemia  (68).  The  miners  disliked  it  because 
of  the  labor  of  removing  it  and  also  because  the  arsenic  in  it  injured  their 
health.  The  first  glassmaker  who  really  understood  the  specific  ability 
of  these  ores  to  impart  a  blue  color  to  glass  was  Christoph  Schiirer  of 
Flatten,  Bohemia,  who,  in  about  the  middle  of  the  sixteenth  century, 
prepared  a  blue  color  for  pottery  at  the  Eulen  smelter  in  Neudeck  ( 69 ) . 
On  a  visit  to  Schneeberg  he  collected  some  pieces  of  the  ore.  When  he 
tested  them  in  his  glass-furnace,  he  found  that  they  fused  with  the  vitreous 
mass  and  yielded  a  handsome  blue  glass.  At  his  plant  in  Neudeck  he 
prepared  the  new  color,  first  for  the  use  of  local  potters  and  later  for 
shipment  to  Nuremberg  and  thence  to  the  Netherlands,  where  the  skilled 
glass-painters  understood  better  how  to  use  it  (68). 

The  poorer  grades  were  used  for  making  bluing  and  blue  starch  for 
laundry  (70).  Roasted  cobalt  ore  was  soon  exported  in  casks  to  eight 
colormills  in  the  Netherlands.  When  the  people  of  Schneeberg  began 
to  remark  that  the  part  of  the  cobalt  ore  which  dropped  down  while 
being  roasted  contained  more  color  than  the  roasted  ore  itself,  Elector 
Johann  Georg  subsidized  the  development  of  an  extensive  cobalt  industry 
there  (68).  A  mixture  of  roasted  cobalt  ore  and  sand,  which  was 
added  to  conceal  its  nature,  was  known  as  Zaffer,  Safflor,  or  Safran.  Most 
of  the  cobalt  ores  in  the  Erzgebirge  also  contained  bismuth,  which  was 
easily  separated  by  liquation. 

After  mentioning  calamine,  Vannoccio  Biringuccio  stated  in  his 
"Pirotechnia"  in  1540:  "Another  similar  half -mineral  is  Zaffer.  It  is  heavy 
like  metal.  It  does  not  melt  by  itself,  but  when  mixed  with  vitreous  sub- 


154  DISCOVERY  OF  THE  ELEMENTS 

stances  it  becomes  like  water  and  colors  them  blue.  Zaffer  is  therefore 
used  for  coloring  glasses  blue  or  for  painting  glass  vessels  with  a  blue 
color.  At  the  artist's  desire,  it  also  serves  as  a  black  pigment  in  these 
crafts,  by  taking  more  of  it  than  is  permissible  for  blue"  (71,  85,  151), 

The  great  sixteenth-century  French  ceramist  Bernard  Palissy  (86) 
once  wrote:  "I  know  no  plant  nor  mineral  nor  any  substance  which  can 
tinge  stones  blue  or  azure  except  saphre,  which  is  a  mineral  earth,  ex 
tracted  from  gold,  silver,  and  copper,  which  has  very  little  color,  except 
gray  inclining  a  little  toward  the  violet.  Whenever  the  said  saphre  is 
incorporated  with  vitreous  substances,  it  makes  a  marvelously  fine  azure: 
hence  one  may  know  that  all  stones  having  an  azure  color  have  taken 
their  tint  from  the  said  saphre"  (72). 

In  his  "Art  of  Glass,"  an  English  translation  of  which  was  published 
in  1699,  Haudicquer  de  Blancourt,  who  was  especially  fond  of  blue 
because  "it  has  resemblance  to  that  of  the  Heavenly  Arch  and  is  taken  for 
the  Symbol  of  Generosity,"  gave  specific  directions  for  the  preparation 
of  metallic  pigments  used  to  tinge  glass  and  "set  it  off  with  an  unspeakable 
Beauty"  (73).  In  his  chapter  on  "The  way  to  prepare  Zaffer  to  tinge 
and  colour  Glass,"  he  quoted  from  Christopher  Merref  s  annotated  trans 
lation  of  Father  Antonio  Nen's  "L'Arte  vetraria": 

"Merret  speaking  of  Zaffer,  and  of  the  Latin  word  Zaffera,  says  it 
comes  from  Germany.  It  is  taken  by  some  for  a  preparation  of  an  Earth 
to  tinge  Glass  blue,  by  others  for  a  Stone,  and  by  him  for  a  Secret; 
asserting  that  there  are  but  few  Authors  who  make  mention  of  it,  and 
no  one  that  tells  us  what  it  is.  ...  Merret  says  Zaffer  is  a  Compound, 
asserting  it  is  neither  Earth  nor  Stone,  .  .  .  That  certainly,  if  it  were 
either  of  these  two,  it  would  have  been  discovered  by  the  Diligence  of 
those  that  have  treated  of  it,  being  of  so  great  use  to  those  who  make 
Glass,  Which  makes  that  Author  say?  the  Zaffer  is  a  Secret,  whereof 
the  Composition  was  found  out  by  a  German.  That  if  he  might  give 
his  Conjecture  of  it,  he  should  think  it  made  of  Copper  and  Sand,  and 
some  proportion  of  Lapis  Calaminaris;  that  the  blue  Colour  it  gives  seems 
to  be  owing  to  the  Brass,  as  that  of  Manganese  to  Iron.  That  only 
Minerals  can  tinge  Glass,  and  that  no  Materials  can  be  found  for  that 
purpose,  except  Metalline  Ones,  Wherefore  he  concludes,  that  the 
matter  which  composes  ZafTer  can  only  be  either  Copper  or  Brass  .  .  ." 
(73). 

Haudicquer  de  Blancourt  then  told  how  Father  Neri  prepared  Zaffer 
by  heating  the  ore  to  redness  in  the  furnace,  sprinkling  it  with  vinegar, 
grinding  it,  and  washing  it  by  decantation  with  warm  water  (73,  74). 
In  his  "Ars  Vitraria  Experimentalis"  Johann  Kunckel  explained  that  the 
acetic  acid  used  in  this  process  was  unnecessary  and  that  the  roasting 


SOME  EIGHTEENTH-CENTUBY   METALS 


155 


Courtesy  Tenney  L.  Davis 

Bernard  Palissy,   1510P-1589.     French   glassmaker,   surveyor,   potter, 
agriculturist,  and  chemist  who  was  familiar  with  "zafEer,"  or  cobalt  blue. 

"Who  is  it  in  the  suburbs  here, 

This  Potter,  working  with  such  cheer,  .  .  . 

This  madman,  as  the  people  say, 

Who  breaks  his  tables  and  his  chairs 

To  feed  his  -furnace  fires  ,  .  . 

O  Palissy!  within  thy  breast 

Burned  the  hot  fever  of  unrest"  ( 82,  152 ) 


of  the  ore  served  to  remove  the  arsenic,  which  was  then  collected,  re- 
sublimed,  and  sold  in  the  apothecary  shops  (70). 

Pierre  Pomet  (Pometius),  a  contemporary  of  Haudicqner  de  Blan- 
court,  described  Zaffer  in  the  section  on  minerals  in  his  "History  of 
Drugs":  "Safre,  or  Zafre,  is  a  Mineral  of  a  Bluish  or  Partridge-Eye 
Colour,  which  the  English,  Dutch,  and  Hamburgers  bring  us  from  the 
East  Indies  and  especially  from  Surat.  .  .  .  Safre  is  much  us'd  by  Delft 


156  DISCOVERY  OF  THE  ELEMENTS 

» 

Ware  and  Glass  Makers,  to  give  a  blue  Colour  to  both  Sorts  of  Ware, 
'Tis  also  with  Safre  that  they  colour  calcin'd  Pewter,  in  order  to  make 
the  false  Stone,  which  IVe  noted  in  the  Chapter  of  Enamels:  And  lastly, 
with  Safre  it  is  that  the  azure  Colour  of  Glass  is  produced,  as  is  before 
observed,  and  of  which  is  made  the  counterfeit  Sapphires"  (117). 

Georg  Biandt,  the  discoverer  of  cobalt,  was  born  in  the  spring  of 
1694  at  Riddarhytta,  Vestmanland,  where  his  father,  Jurgen  Brandt,  a 
former  apothecary,  operated  a  copper  smelter,  an  ironworks,  and  some 
mines.  At  an  early  age  Georg  began  to  help  his  father  with  his  chemical 
and  metallurgical  experiments.  He  studied  medicine  and  chemistry  for 
three  yeais  at  Leyden  under  the  famous  Herman  Boerhaave  and  received 
his  degiee  of  doctor  of  medicine  at  Reims  in  1726.  Although  he  never 
carried  on  a  general  practice,  he  was  one  of  the  physicians  called  to  the 
deathbed  of  Fredrik  I  (5,  6,  34). 

On  his  way  home  from  the  Netherlands  he  studied  mining  and  metal 
lurgy  in  the  Harz,  and  in  1727  he  was  placed  in  charged  of  the  chemical 
laboratory  at  the  Bureau  of  Mines  in  Stockholm,  which  was  then  in  poor 
financial  condition.  After  the  laboratory  was  sold,  Brandt  and  his  stu 
dents  Henrik  Teofil  Scheffer  and  Axel  Fredrik  Cronstedt  carried  on  their 
epoch-making  researches  at  the  Royal  Mint,  and  in  1730  Brandt  became 
assay  master  of  the  Mint.  Three  years  later  he  published  a  systematic 
investigation  of  arsenic  and  its  compounds  in  which  he  showed  that 
arsenic  is  a  "semi-metal"  and  that  "white  arsenic"  [arsenious  oxide]  is  its 
calx  (35). 

Brandt's  most  important  contribution  to  science  was  his  discovery 
of  the  element  cobalt.  Since  the  mineral  which  had  been  used  since 
the  sixteenth  century  for  making  "Zaffer,"  or  smalt,  resembled  copper 
ores  in  its  ability  to  give  blue  solutions  when  dissolved  in  acids,  yet  (even 
in  minute  amounts)  imparted  a  much  deeper  blue  color  to  glass  than 
copper  compounds  do,  it  was  called  "cobalt"  from  the  German  word 
Kobold,  meaning  subterranean  gnome.  These  little,  teasing  earth  sprites 
are  frequently  mentioned  in  Goethe's  "Faust": 

Salamander  soil  gluhen  Salamander  shall  kindle, 

Undene  sich  winden,  Writhe  nymph  of  the  wave, 

Sylphe  verschwinden,  In  air  sylph  shall  dwindle, 

Kobold  sich  muhen.  And  Kobold  shall  slave 

Wer  sie  nicht  kennte  Who  doth  ignore 

Die  Elemente,  The  piimal  Four, 

Ihre  Kraft,  Nor  knows  aright 

Und  Eigenschaft,  Their  use  and  might, 

Ware  kein  Meister  O'er  spirits  will  he 

tfber  die  Geister.    (8)  Ne'er  master  'be.     (8) 


SOME  EIGHTEENTH-CENTURY  METALS  157 

The  Kobolds,  according  to  an  ancient  German  superstition,  delighted 
in  destroying  the  work  of  the  miners,  causing  them  endless  trouble;  and 
in  mining  towns  the  people  used  to  pray  in  the  churches  for  deliverance 
from  the  power  of  these  malicious  spirits  (7). 

In  1730  or  before,  Georg  Brandt  prepared  a  dark  blue  pigment  from 
an  ore  found  at  the  Skil£  copper  works  ( Riddarhytta )  in  Westmanland 
(39).  Specimens  of  this  "fargcobalt"  are  still  preserved  in  the  Cederbaum 
collection  at  Oskarshamn.  Since  the  first  accurate  description  of  metallic 
cobalt  is  to  be  found  in  Brandt's  dissertation  on  the  half-metals  in  the 
Acta  Literaria  et  Scientiarum  Sueciae  for  1735,  it  has  frequently  been 
stated  that  cobalt  was  discovered  in  that  year.  Nils  Zenz6n  has  shown, 
however,  that  this  issue  of  the  Acta  was  not  published  until  1739  and  that 
the  portion  of  Brandt's  "Diarium  Chymicum"  which  records  his  researches 
fiom  the  latter  part  of  1737  to  the  end  of  1738  is  merely  a  Swedish  edition 
of  the  "Dissertatio  de  semi-metallis." 

According  to  Zenzen,  Brandt  stated  in  his  diary  for  1741  ( which  was 
not  edited  until  1744)-  "As  there  are  six  kinds  of  metals,  so  I  have  also 
shown  with  reliable  experiments.,  in  my  dissertation  on  the  half-metals 
which  I  presented  to  the  Royal  Academy  of  Sciences  in  Upsala  in  1735, 
that  there  are  also  six  kinds  of  half -metals.  The  same  dissertation  shows 
that  I,  through  my  experiments,  had  the  good  fortune  .  .  to  be  the  first 
discoverer  of  a  new  half -metal,  namely  cobalt  regulus,  which  had  formerly 
been  confused  with  bismuth  .  .  /'  (39).  Zenzen  believes,  however,  that 
this  date  must  be  attributed  to  Brandt's  lack  of  memory.  After  separat 
ing  this  metal  by  fire  assay,  he  named  it  cobalt  for  the  mineral  from 
which  he  had  extracted  it  In  his  "Dissertation  on  the  semi-metals" 
Brandt  stated  that  six  metals  and  six  "half -metals"  (mercury,  bismuth,  zinc, 
and  the  reguluses  of  antimony,  cobalt,  and  arsenic)  were  then  known. 
By  a  "half-metal"  he  meant  a  substance  which  resembles  the  metals  in 
color,  weight,  and  form  but  which  is  not  malleable.  Since  most  bismuth 
ores  contain  cobalt,  he  gave  six  ways  of  distinguishing  between  these 
two  "semi-metals." 

"1.  When  bismuth  is  broken  with  a  hammer,  it  gives  a  fracture  com 
posed  of  little  super-imposed  laminae.  The  regulus  of  cobalt  is  more 
like  a  true  metal  Moreover  there  is  a  very  great  difference  in  the  color 
of  these  two  metals,  .  ,  . 

"2.  In  fusing  they  do  not  mingle  at  all  with  each  other,  it  is  easy  to 
separate  them  with  a  stroke  of  the  hammer;  for  they  are  attached  about 
as  an  almond  is  to  its  stone,  and  in  this  union  they  seem  to  be  separated 
by  a  segment  of  a  circle  so  that  they  both  appear  to  form  but  a  single 
regulus,  at  one  end  of  which  is  found  the  bismuth,  or  marcasite,  and  at 
the  other  the  regulus  of  cobalt. 


158  DISCOVERY  OF  THE  ELEMENTS 

"3.  The  regulus  of  cobalt,  pulverized  and  calcined,  gives  when  one 
fuses  it  with  flint  and  fixed  alkali,  a  blue  glass,  known  under  the  names 
zaffera,  sasre,  or  smalt.  Marcasite  does  not  give  any  smalt.  The  blue 
glass  which  bismuth  ore  sometimes  gives  is  produced  by  the  cobalt  which 
is  almost  always  found  in  the  ores  of  this  semi-metal. 

"4,  Bismutih  melts  easily;  when  kept  fused,  it  becomes  calcined  like 
lead  and  converted  into  a  yellow  powder,  which,  when  melted,  gives  a 
glass  of  the  same  color  as  that  of  lead.  .  .  . 

"5.  Bismuth  amalgamates  with  mercury;  which  the  regulus  of  cobalt 
does  not  do  at  all. 

"6.  Bismuth  dissolves  in  nitric  acid  and  in  aqua  regia;  both  solutions 
are  precipitated  by  pure  water  in  the  form  of  a  white  powder.  When  the 
regulus  of  cobalt  is  dissolved  in  these  menstrua,  it  cannot  be  precipitated 
from  them  except  by  the  alkalies;  fixed  alkali  precipitates  it  in  the  form 
of  a  powder  which,  after  being  washed,  remains  dark  and  black;  whereas 
when  one  precipitates  it  with  volatile  alkali,  especially  if  it  has  been 
dissolved  by  aqua  regia,  it  acquires  a  very  red  color,  which  changes 
to  blue,  if  one  exposes  it  to  the  fire  up  to  the  point  of  redness"  (27} . 

Brandt  later  made  a  more  complete  investigation  of  cobalt.  He  also 
demonstrated  that  common  salt  and  soda  contain  the  same  (mineral) 
alkali,  whereas  saltpeter  contains  the  vegetable  alkali  (potash).  This 
confirmed  the  earlier  work  of  Duhamel  du  Monceau.  Brandt  encouraged 
the  use  of  Swedish  zinc  in  the  manufacture  of  brass.  In  1748  he 
demonstrated  before  Crown  Prince  Adolf  Fredrik  and  the  Royal  Swedish 
Academy  of  Sciences  that  gold  can  be  made  to  dissolve  in  hot  nitric  acid 
in  a  closed  vessel  but  that  when  the  solution  is  shaken  in  presence  of 
air  the  gold  precipitates  out  (87).  Since  Brandt  prepared  his  nitric  acid 
from  saltpeter  and  sulfuric  acid  it  probably  contained  some  of  the  latter. 
This  discovery  shed  light  on  some  of  the  alleged  transmutations  of 
silver  to  gold  and  was  an  important  step  in  the  triumph  of  pure  science 
over  alchemy.  In  the  opinion  of  C,  W.  Oseen,  "No  Swedish  chemist  did 
more  than  Georg  Brandt  for  the  combating  of  alchemy'*  (87).  When 
Brandt  died  at  Stockholm  on  April  29,  1768,  his  death  was  mourned  by 
the  entire  scientific  world.  He  was  one  of  the  ablest  chemists  of  his 
time  (6). 

A.  F.  Cronstedt  once  spoke  eloquently  of  "what  a  Brandt  in  our 
time  can  accomplish  in  cramped  quarters,  with  broad  knowledge  and 
with  zeal  which  even  age  cannot  check.  This  honored  man,  whose  pres 
ence  here  prevents  me  from  saying  what  I  wish,  received  chemistry  and 
its  instruments  (already  rusting  after  Hjarne's  death)  with  newer  views 
in  natural  science,  with  thorough  mathematical  knowledge,  and  with 
systematic  order  such  as  his  master  Herman  Boerhaave  of  Leyden  had 


SOME  EIGHTEENTH-CENTURY  METALS  159 

employed.  Thereafter,  followed  only  experiments  which  all  scholars 
could  apply  to  experimental  physics  and  from  which  husbandry  could 
quickly  benefit.  The  science  was  presented  as  clearly  as  it  had  formerly 
been  made  obscure,  and  from  that  day,  it  has  gradually  gained  the 
right  to  instruct  the  youth  in  our  universities,  to  the  great  gain  of  both 
parties"  (75). 

After  Anton  von  Svab  and  Georg  Brandt  had  died  in  the  same  year, 
Carl  von  Linn6  said:  "The  kingdom  and  our  sciences  have  now  lost  in 
a  single  year  two  stars  of  the  first  magnitude,  Brandt  and  Svab.  The 
Bureau  of  Mines  and  the  science  of  mining  have  lost  their  supporting 
pillars.  Men  such  as  these  never  spring  up  like  mushrooms.  So  far  as 
I  know,  Europe  has  none  like  them.  ...  A  king  can  lose  an  army,  but 
within  a  year  have  another  ]ust  as  good.  A  king  can  lose  a  fleet  and 
within  two  years  have  another  rigged  up,  but  a  Brandt  and  a  Svab  cannot 
be  gotten  again  during  his  entire  reign"  (52).  The  history  of  the  Swedish 
Academy  of  Sciences  describes  Brandt  as  "frugal,  taciturn,  and  solitary" 
(76), 

In  1776  a  Hungarian  chemist,  Petrus  Madacs,  defended  a  thesis  in 
which  he  claimed,  as  did  J.  J.  Winterl,  that  cobalt  is  a  compound  of 
iron  and  arsenic,  but  admitted  that  nickel  is  an  element.  He  distinguished 
clearly  between  copper  and  nickel  and  stated  that  "copper  and  arsenic 
never  give  nicker  (77). 

Although  chemists  long  disputed  the  elemental  nature  of  cobalt, 
perhaps  because  they  were  unable  to  reduce  the  blue  smalt  to  the  metal, 
Torbern  Bergman  explained  in  1780  that,  because  of  the  high  coloring 
power  of  cobalt,  only  a  small  amount  of  it  need  be  present  in  smalt.  He 
heated  many  kinds  of  cobalt  glass  with  black  flux  and  was  able,  in  each 
case,  to  obtain  the  metal,  but  only  in  small  amounts  (78).  He  dis 
tinguished  definitely  between  nickel  and  cobalt,  stated  that  nickel  never 
gives  a  blue  glass  nor  a  sympathetic  ink  nor  a  red  solution  in  acids  and 
that  cobalt  never  gives  a  green  one,  and  that  pure  nickel  readily  alloys 
with  silver,  whereas  cobalt  does  not  (78).  From  experiments  with  the 
preparation  of  smalt  and  sympathetic  ink  in  the  following  year,  Sven  Rin- 
man  also  concluded  that  cobalt  and  nickel  are  two  entirely  different  metals 
(79). 

In  1736  the  brothers  Henric  and  Olof  Kalmeter  discovered  at  Los, 
Farila  parish,  Halsingland,  a  cobalt  ore  which  they  at  first  exported  in 
this  form.  In  1744,  however,  a  smalt  works  employing  skilled  workers 
from  Germany  was  built  there  (39). 

Shortly  before  this,  Georg  Brandt  had  discovered  a  new  cobalt 
mineral  at  the  Goran  Mine  at  Bastnas,  near  Riddarhytta.  "My  curiosity," 
said  he,  "did  not  allow  me  to  postpone  the  chemical  investigation  until 


160  DISCOVERY  OF  THE  ELEMENTS 

my  return  to  Stockholm;  I  therefore  began  it  immediately,  so  far  as  my 
instruments  permitted"  (118).  When  he  calcined  the  mineral  strongly, 
he  noticed  an  odor  of  sulfuric  acid  but  no  sulfur  flame,  and  drew  the 
incorrect  conclusion  that  the  ore  must  be  a  sulf ate.  With  a  simple  forge 
and  bellows  he  prepared  metal  from  it,  and  on  his  return  to  Stockholm 
he  prepared  a  blue  glass  by  fusing  the  ore  with  flint  and  alkali.  Since 
the  ore  had  a  high  iron  content,  the  regulus  contained  more  iron  than 
cobalt.  He  observed  that  "some  cobalt  regulus  mixed  with  the  iron 
does  not  make  it  brittle  even  after  cooling  and  that  it  remains  as  ductile 
as  before,  yet  at  the  same  time  hard  and  tenacious.  On  the  other  hand 
I  have  found  that,  when  arsenic  and  iron  are  combined  in  the  form  of 
a  regulus,  they  yield  a  mass  as  brittle  as  chilled  cast  iron"  (118). 

Brandt  published  a  description  of  this  mineral  in  the  volume  of  the 
Acta  of  the  Upsala  Academy  for  1742  and  in  Vetenskapsacademiens 
Uandlingarna  for  1746,  and  mentioned  that  it  contains  cobalt,  iron,  and 
sulfur,  but  that,  unlike  ordinary  cobalt  glance,  it  is  free  from  arsenic. 
When  W.  von  Hisinger  made  a  quantitative  analysis  of  it  in  1810,  he 
found  it  to  be  cobalt  sulfide.  This  mineral  is  now  known  as  linnaeite;  its 
formula  is  Co3S4,  in  which  part  of  the  cobalt  may  be  replaced  by  nickel, 
iron,  or  copper. 

Sympathetic  Ink.  Although  the  discovery  of  the  cobalt  sympathetic 
ink,  which  remains  invisible  until  warmed,  has  often  been  attributed  to 
Jean  Hellot,  who  first  made  it  known  publicly,  he  was  not  the  first 
person  to  prepare  it.  Hellot  himself  stated  that  a  German  artist  of  Stol- 
berg  had  shown  him  a  reddish  salt  which,  when  exposed  to  heat,  became 
blue.  It  had  been  prepared  by  dissolving  Schneeberg  cobalt  in  aqua 
regia  (119)-  H.  F.  Teichmeyer  of  Jena  was  also  familiar  with  this  cobalt 
ink,  perhaps  even  before  Hellot  made  its  composition  public  in  1737 
(119). 

Johann  Beckmann  stated,  in  his  "History  of  Inventions,  Discoveries, 
and  Origins,"  that  a  German  lady  mentioned  by  Pot  [J.  H.  Pott]  in  his 
"Observ.  Chym.  Collectio  prima"  in  1739  (page  163),  published  the  recipe 
for  this  sympathetic  ink  in  1705  in  a  book  which  Pott  quotes  "under  the 
unintelligible  title  of  D.  J.  W.  in  clave"  (119).  Hermann  Kopp  ex 
plained  that  the  author  of  this  "Key  to  the  cabinet  of  Nature's  secret 
treasury"  was  Dr.  Jacob  Waitz,  physician  in  ordinary  at  Gotha,  Germany 
(120),  All  these  early  recipes  specified  the  use  of  bismuth  ores.  Dr. 
Johann  Albrecht  Gesner  of  Wurttemberg  showed  in  1744,  however,  that 
this  peculiar  ink  was  produced  not  from  the  bismuth  itself  but  from  the 
cobalt  present  in  the  ore  (120). 

Cobalt  in  Meteorites,  The  Quarterly  Journal  of  Science  and  the  Arts 
for  1819  has  a  note  on  the  discovery  of  cobalt  in  meteorites:  "M.  Stro- 


SOME  EIGHTEENTH-CENTUBY   METALS  161 

meyer  has  discovered  cobalt  in  those  masses  of  matter  of  meteoric  origin, 
but  it  is  uncertain  whether  it  is  constantly  present  or  not.  The  mass  in 
which  M.  Stromeyer  has  detected  it  is  that  at  the  Cape  of  Good  Hope; 
but  he  could  find  none  in  the  specimen  discovered  in  Siberia  by  Pallas, 
nor  in  that  of  EUenbogen  [Elbogen]  in  Bohemia.  Klaproth  is  the  only 
chemist  who  had  previously  observed  appearances  which  justified  the 
opinion  that  meteoric  stones  contained  cobalt,  and  the  stone  in  which 
he  remarked  it  was  that  which  fell  at  Aichstaedt  in  1785"  (121).  Smith- 
son  Tennant  had  previously  detected  the  presence  of  nickel  in  this 
meteoric  iron  which  Stromeyer  analyzed  (122). 

Cobalt  in  Nutrition,  Johan  Georg  Forchhammer  found  in  his  great 
research  on  the  composition  of  sea  water  that  marine  organisms  concen 
trate  the  substances  necessary  for  their  existence  and  thus  provide  the 
chemist  with  a  delicate  indirect  means  of  detecting  certain  elements 
which  occur  in  sea  water  in  very  minute  amounts.  He  discovered  co 
balt,  for  example,  in  the  ashes  of  Zostera  marina  and  in  the  fossil  Sponges 
of  the  chalk  (123). 

M,  O.  Schultze  stated  that  cobalt  is  an  essential  element  for  the 
nutrition  of  sheep  and  cattle.  Although  it  is  not  essential  for  the  growth 
of  the  herbage  plants,  they  nevertheless  take  it  up  from  the  soil  and  make 
it  available  for  animal  nutrition  ( 106 )  To  prevent  anemia,  even  when  the 
diet  contains  adequate  amounts  of  iron,  a  small  amount  of  cobalt  (not 
more  than  four  micrograms  per  day  per  kilogram  of  body  weight  of 
sheep)  is  required  (124).  It  is  an  important  constituent  of  vitamin  B]2. 


NICKEL 

Axel  Fredrik  Cronstedt,  the  discoverer  of  nickel,  was  born  on  Decem 
ber  23,  1722,  at  Stroppsta,  Tunnge  parish,  in  the  p  -ovince  of  Soderman- 
land  in  Sweden  (5).  His  father,  a  lieutenant-general,  gave  him  a  good 
education,  and  the  boy  soon  demonstrated  his  ability  in  physical  science 
and  mathematics.  As  a  child  he  studied  at  home  under  private  tutors 
and  became  especially  interested  in  mathematics,  natural  sciences.,  and 
drawing.  In  J.  G.  Wallerius'  classes  in  mineralogy  and  chemistry  at 
Upsala  he  became  acquainted  with  Sven  Rinman,  who  aroused  his 
enthusiasm  for  a  career  in  mining.  In  1744-45  Cronstedt  visited  the 
most  important  mines  in  Sweden,  and  at  the  Sala  mine  gained  a  first-hand 
knowledge  of  the  metallurgy  of  lead  and  silver.  From  1746  to  1748  he 
studied  assaying  and  chemistry  under  Georg  Brandt  He  rendered  great 
service  to  his  country  as  a  metallurgist  in  the  Bureau  of  Mines,  and  his 
name  will  always  be  honored  because  of  the  brilliant  manner  with  which 
he  discovered  the  useful  metal  nickel  (6\  24). 


162 


DISCOVERY  OF  THE  ELEMENTS 


The  history  of  this  metal  is  similar  to  that  of  cobalt.  An  alloy  of  nickel 
called  packfong  (or  paktong)  was  used  by  the  Chinese  long  before  the 
metal  was  known  in  Europe  ( 7,  23 ) ,  In  Germany  a  heavy,  reddish  brown 
ore,  frequently  found  covered  with  green  spots  or  stains,  was  used  to 
color  glass  green;  the  miners  called  it  Kupfernickel  (21).  Since  Nickel, 
like  Kobold,  means  deceptive  little  spirit,  the  word  Kupfernickel  may  be 
translated,  false  copper.  Urban  Hiarne,  in  a  work  on  metals  published  in 


Urban  Hiarne,  1641-1724.  Swedish  physician,  mineralogist,  and  poet.  Assessor  and 
later  acting  president  of  the  Swedish  Bureau  of  Mines.  Author  of  "Regium  Labora- 
tonum  Chymicum,"  Stockholm,  1683.  In  1694  he  mentioned  the  ore  Kupfernickel,  in 
which  Cronstedt  more  than  half  a  century  later  discovered  nickel.  See  also  ret.  (84). 


1694,  expressed  a  belief  that  Kupfernickel  was  a  kind  of  cobalt  or  arsenic 
mixed  with  copper,  but  in  this  view  there  was  only  a  germ  of  truth  ( 7,  24 ) . 
A  F.  Cronstedt  once  said,  "Hiarne  in  his  lifetime  pursued  chemical 
research  most  zealously.  With  all  his  creative  genius  and  his  desire  to 
support  Cartesian  natural  science  with  chemical  arguments  and  con 
clusions,  he  still  did  not  fail  to  consider  the  practical  use  which  industry 
could  demand  of  it.  With  the  support  of  the  authorities,  he  therefore 
occupied  himself  with  the  testing  and  investigation  of  substances  from  all 
realms  of  nature  and  all  parts  of  the  country"  (75).  With  Hiarne,  ac 
cording  to  Sten  Lindroth,  ''Swedish  chemistry  attained  international  fame 
for  the  first  time"  (8S). 

Although  no  one  had  ever  succeeded  in  extracting  copper  from 
Kupfernickel,  J.  H.  Linck  (or  Link)  stated  in  1726  that,  since  it  gives 
green  solutions  when  dissolved  in  nitric  acid,  it  must  be  a  cobalt  ore 


SOME  EIGHTEENTH-CENTXJRY   METALS  163 

containing  copper  (24,  80).  When  Swedish  cobalt  miners  found  a  reddish 
yellow  ore  which  imparted  little  or  no  blue  color  when  fused  with  glass 
frit,  they  called  it  "cobalt  which  had  lost  its  soul"  (21 ). 

In  1751  Axel  Fredrik  Cronstedt  investigated  a  new  mineral  which  he 
found  in  the  cobalt  mine  at  Los,  Farila  parish,  Halsingland  (21).  When 
he  began  this  research  he  was  not  yet  thirty  years  of  age.  In  one  of  his 
experiments  he  placed  a  piece  of  iron  in  the  acid  solution  of  the  ore, 
expecting  to  see  the  copper  deposit  on  it.  To  his  great  surprise,  he  was 
unable  to  secure  a  deposit  of  any  kind,  for,  as  is  now  well  known,  niccolite 
contains  no  copper  (9).  Upon  calcining  the  green  crystals  which  covered 
the  surface  of  some  weathered  Kupfernickel,  and  reducing  the  calx;  or 
oxide,  by  heating  it  with  charcoal,  Cronstedt  obtained  a  white  metal  bear 
ing  no  resemblance  whatever  to  copper.  After  studying  its  physical, 
chemical,  and  magnetic  properties,  he  announced  in  the  Memoirs  of  the 
Stockholm  Academy  that  he  had  discovered  a  new  metal,  different  from 
all  others,  for  which  he  proposed  the  name  nickel  (7,21}. 

He  said, 

This  salt  or  this  vitriol,  after  having  been  calcined,  gives  a  colcothar  or 
clear,  gray  residue  which,  when  fused  with  three  parts  of  black  flux,  gives  a 
regulus  of  50  pounds  per  quintal.  This  regulus  is  yellowish  on  the  outside,  but 
in  the  fracture  it  is  silver-colored  with  iridescent  colors,  and  composed  of  little 
laminae,  quite  similar  to  those  of  bismuth.  It  is  hard  and  brittle,  only  feebly 
attracted  by  the  magnet;  calcination  changes  it  to  a  black  powder;  these  two 
properties  come  from  the  iron  which  has  passed  into  the  vitriol.  This  regulus 
dissolves  in  aqua  fortis,  aqua  regia,  and  spirit  of  salt;  it  gives  on  dissolving  a< 
brilliant  green  color,  and  there  precipitates  a  black  powder  which,  when  heated 
before  the  enamelers'  blowpipe,  gives  signs  of  phlogiston  and  of  the  metallic. 
part  which  it  contains  .  .  .  (7,  21 ) . 

The  slight  magnetization  observed  by  Cronstedt  is  a  property  of  nickel 
itself.  In  1751  he  mixed  some  Kupfernickel  with  "black  flux"  placed 
the  mixture  in  a  crucible,  and  covered  it  with  a  layer  of  common  salt, 
Upon  roasting  it  he  not  only  reduced  the  oxide  to  the  metallic  state,  but 
melted  the  metal.  "I  made  many  attempts,"  said  he,  "to  mix  whole  and 
half  metals  for  the  purpose  of  preparing  a  product  like  it;  but  without 
success.  I  have  therefore  employed  Herr  Director  Scheffer's  rich  insight 
and  untiring  efforts  to  the  same  end,  but  all  his  observations  have  as  yet 
given  no  due."  Cronstedt  therefore  concluded  that,  if  no  one  of  the 
twelve  known  "whole  and  half  metals"  nor  any  mixture  of  them  could 
duplicate  the  properties  of  the  regulus  which  remained  after  the  removal 
of  the  iron  and  cobalt,  he  would  have  to  regard  it  as  a  new  half -metal  ( 21 ) . 
Not  until  1754  did  he  publicly  christen  it.  "The  greatest  quantity  of  the 


164  DISCOVERY  OF  THE  ELEMENTS 

new  previously  described  half  metal,"  said  he,  "is  contained  in  Kupfer- 
nickel;  therefore  I  retain  the  same  name  for  its  regulus  or  call  it  nickel 
for  short.  For  my  experiments  I  have  used  a  massive  Kupfernickel  from 
the  Kuhschacht  [Cow  Shaft]  in  Freiberg,  Saxony"  (21).  Kupfernickel, 
or  niccolite,  is  now  known  to  be  an  arsenide  of  nickel. 

Cronstedt  pointed  out  that  nickel  and  cobalt  are  closely  associated 
in  nature  and  that  the  speiss  which  falls  to  the  bottom  of  the  pots  in 
which  cobalt  is  vitrified  in  the  manufacture  of  saffre  is  composed  mainly 
of  nickel  containing  more  or  less  cobalt,  iron,  sulfur,  and  arsenic. 

Many  chemists  in  Sweden  and  in  other  parts  of  the  world  immediately 
accepted  Cronstedt's  claim  to  the  discovery  of  a  new  element,  but  B.-G. 
Sage  (22)  and  A.-G.  Monnet  in  France  believed  that  his  nickel  was  merely 
a  mixture  of  cobalt?  arsenic,  iron,  and  copper  (7).  As  a  matter  of  fact, 
it  was  somewhat  contaminated  with  iron,  cobalt,  and  arsenic,  and  there- 


Balthasar-Georges      Sage,      1740-1824. 

French  analytical  and  mmeralogical 
chemist  of  the  phlogistic  school.  In  his 
"Analyse  Chimique,"  published  in  1786, 
he  gave  methods  of  testing  and  ana 
lyzing  coal,  clay,  water,  and  many 
minerals. 


fore  the  great  pioneer  in  analytical  chemistry  Torbern  Bergman  carried 
out  an  elaborate  series  of  experiments  by  means  of  which  he  obtained 
nickel  in  a  high  state  of  purity.  The  results  he  published  in  1775  com 
pletely  confirmed  those  of  Cronstedt,  for  he  showed  that  no  combination 
of  iron,  arsenic,  cobalt,  and  copper  will  duplicate  the  properties  of  nickel, 
Bergman's  pupil  Johan  Arvidsson  Afzelius  defended  these  views  at  Upsala 
in  1775  (7,36). 

Even  after  this  proof,  some  chemists  were  very  conservative  about 
accepting  the  new  element.  William  Nicholson,  in  his  "First  Principles 
of  Chemistry"  published  in  1796?  gave  the  following  account  of  it: 


SOME  ElCHraEKtH-CENTtTRY    METALS 


This  metallic  substance  has  not  been  applied  to  any  use;  and  the  chief  at 
tention  of  those  chemists  who  have  examined  it  has  been  directed  to  obtain  it 
m  a  state  of  purity,  which,  however,  has  not  yet  been  accomplished.  .  . 
Nickel  has  been  thought  to  be  a  modification  of  iron.  ...  So  long  as  no  one 
is  able  to  produce  this  metal  from  pure  iron  or  copper,  and  to  explain  in  an  in 
telligible  way  the  process  by  which  it  can  be  generated,  we  must  continue  to 
legard  it  as  a  peculiar  substance,  possessing  distinct  propeities.  The  general 
opinions  of  chemists  concur  in  admitting  the  force  of  this  reasoning  (10). 

Cronstedt's  fame  does  not  rest  alone  on  his  discovery  of  nickel.  One 
of  his  greatest  contributions  to  science  was  the  treatise  in  which  he 
reformed  mineralogy  and  classified  mineials  not  merely  according  to  their 
external  properties,  such  as  form,  hardness,  and  color,  but  also  according 
to  their  chemical  composition,  This  treatise  was  translated  into  several 
languages.  Berzelius  said  of  him,  "Cronstedt,  the  founder  of  the  chemical 
system  of  mineralogy,  a  man  who  by  his  acuteness  in  that  science  rose  so 
far  above  his  age  that  he  was  never  correctly  understood  by  it,  used  the 
blowpipe  to  distinguish  between  minerals"  (11).  Ability  to  use  this 
instrument  skillfully  and  without  fatigue  and  injury  to  health  required,  as 
Berzelius  pointed  out,  an  intensive  training  that  few  chemists  care'  to 
undergo  (83).  Nevertheless,  Cronstedt  acquired  such  unusual  control 
over  it  that  he  could  direct  a  candle-flame  upon  a  sample  no  larger  than 
the  head  of  a  pin  and  make  it  white-hot  (11). 

Jagnaux  stated  that  Cronstedt  and  Rinman  operated  a  successful  plant 
for  distilling  zinc,  and  that  they  "were  as  well  versed  in  metallurgy  as 
in  mineralogy"  (4).  Cronstedt  also  discovered  a  zeolite,  one  of  the  sili 
cates  so  widely  used  for  softening  water,  and  wrote  a  paper  on  it  in  1756. 
He  died  in  Saters  parish  near  Stockholm  on  August  19,  1765  (32), 

Nickel  in  Meteorites.  Centuries  before  the  discovery  of  nickel,  primi 
tive  peoples  shaped  meteoric  iron  into  implements  and  swords  and  appre 
ciated  the  superiority  of  this  Heaven-sent  metal  (125).  In  1777  J.  K.  F. 
Meyer  of  Stettin  noticed  that  when  he  added  sulfunc  acid  to  some  native 
iron  which  P.  S.  Pallas  had  found  in  Siberia,  he  obtained  a  green  solution 
which  became  blue  when  it  was  treated  with  ammonium  hydroxide.  In 
1799  Joseph-Louis  Proust  detected  nickel  in  meteoric  iron  from  Peru 
(126),  This  grayish  white  native  iron  had  been  observed  by  Rubin  de 
Celis.  Since  it  did  not  rust,  it  was  sometimes  mistaken  for  native  silver. 

Led  by  the  deep  green  color  of  its  solutions  to  suspect  the  presence 
in  it  of  copper,  Proust  passed  hydrogen  sulfide  into  an  acidic  solution  of 
the  iron,  but  obtained  no  precipitate.  Believing  that  only  nickel  could 
produce  such  an  effect,  he  removed  the  iron  as  hydrous  ferric  oxide  and 
prepared  nickel  sulf  ate  from  the  filtrate,  These  experiments  are  described 
in  Nicholsons  Journal  for  November,  1800:  "The  native  iron  of  Peru  is 


166  DISCOVEKY  OF  THE  ELEMENTS 

therefore,  according  to  the  experiments  made  by  M.  Proust,  an  alloy  of 
iron  and  nickel,  a  new  discovery  of  the  most  interesting  nature.  The 
presence  of  nickel  in  this  alloy,  observes  the  author,  appears  to  announce 
that  it  is  the  product  of  art;  but  when  it  is  considered  that  there  exists 
a  mass  of  more  than  1363  mynagrams  (300  quintals)  in  a  plain  of  more 
than  100  leagues  in  circumference,  where  there  is  neither  mountain  nor 
water,  nor  scarcely  a  stone  is  to  be  found,  the  difficulty  of  the  problem 
still  remains  in  all  its  force  Lastly,  adds  M.  Proust,  if  the  power  of 
uniting  these  metals  in  suitable  proportions  can  be  obtained  by  metallur 
gists,  they  will  have  obtained  an  alloy  which  will  possess  many  advantages 
over'other  iron,  and  more  particularly  that  of  not  being  able  to  rust"  (127) 

In  1805  James  Soweiby  received  a  piece  of  meteoric  iron  which 
Captain  Barrow  had  found  "about  two  hundred  miles  within  the  Cape 
of  Good  Hope."  When  Smithson  Tennant  analyzed  it,  he  found  about  10 
per  cent  of  nickel  in  it.  Mr.  Sowerby  had  the  metal  hammered  into  a 
sword,  which  he  presented  to  the  Emperor  of  Russia  (128). 

Some  Famous  Nickel  Mines  and  Smelters.  The  nickel  smelting  works 
near  Schneeberg  in  the  Saxon  Erzgebiige  date  from  1642.  They  produced 
nickel,  cobalt,  arsenic,  and  bismuth  from  the  local  ores,  and  refined  the 
nickel-cobalt  regulus  imported  from  the  Modum  works  in  southern  Nor 
way  (129). 

French  explorers  worked  the  La  Motte  Mine  in  Missouri  for  nickel 
as  early  as  1719  and  during  the  period  from  1830-50  shipped  the  metal 
to  refiners  in  England  (125).  Before  the  mining  of  nickel  ores  on  the 
island  of  New  Caledonia  in  the  Pacific  was  well  developed  in  about  1877, 
nickel  was  so  scarce  that  oies  containing  as  little  as  one  per  cent  of  it  could 
be  worked  profitably  (125),  The  greatest  nickel  deposits  in  the  world, 
those  of  the  Sudbuiy  district  of  Ontario,  Canada,  were  discovered  in 
about  1856  (23,125). 

Early  Nickel  Alloys.  In  1776  Assessor  Gustaf  von  Engestrom,  an 
assay  master  who  had  studied  under  H.  T.  Scheffer,  A.  F.  Cronstedt, 
Anton  von  Svab,  and  A.  S,  Marggraf,  found  that  the  Chinese  alloy  pack- 
fong  contained  copper,  nickel,  and  zinc.  This  sonorous,  white  metal  was 
called  pac/cfong  (white  copper)  to  distinguish  it  from  tongfong  (red 
copper)  When  Engestrom  and  Peter  Johan  Bladh  of  the  Swedish  East 
India  Company  tested  the  untreated  metal,  they  found  it  to  be  made 
from  a  natural  alloy  of  nickel,  copper,  and  a  very  little  cobalt,  which  was 
probably  an  accidental  impurity.  This  crude  metal  from  complex  copper- 
nickel  sulfide  ores  of  Yunnan,  southern  China,  was  shipped  to  Canton  in 
the  form  of  "three-cornered  rings"  8  or  9  inches  in  outer  diameter  and 
about  1V2  inches  thick  (21, 125).  Engestrom  believed  it  must  have  been 
smelted  from  nickeliferous  copper  ores.  The  natural  mixture  had  a  red- 


SOME  EIGHTEENTH-CENTURY   METALS  167 

dish  color,  but  in  Canton  another  metal  was  added  to  it  to  make  it  per 
fectly  white;  and  many  craftsmen  worked  it  up  into  household  utensils 
such  as  spoons,  dishes,  snuffboxes,  lamps,  etc.  Engestrom  found  by  exper 
iment  that  the  metal  added  at  Canton  must  have  been  zinc. 

He  stated  that  the  alloy  was  suitable  for  ornamental  articles  which 
would  not  come  into  contact  with  acid  or  salt  and  that  if  the  copper, 
nickel,  and  cobalt  ores  from  Riddarhytta,  Hakansboda,  Tunaberg,  etc. 


Torbern  Bergman,  1735-1784.  Swedish 
chemist,  mineralogist,  and  editor. 
Author  of  the  "Opuscula  physica  et 
chemica,"  a  six-volume  treatise.  Among 
bis  students  were  Gahri,  the  discoverer 
of  manganese,  Hjelm,  who  isolated 
molybdenum,  and  J.  J  de  Elhuyar,  who 
with  his  brother  Fausto  discovered 
tungsten. 


could  be  made  free  from  arsenic,  it  ought  to  be  possible  to  manufacture 
the  alloy  in  Sweden.  Cobalt,  he  thought,  would  serve  the  same  purpose 
as  the  nickel  (130).  He  loved  to  collect  minerals  from  the  East  Indies. 
Since  he  was  the  translator  of  Cronstedt's  mineralogy,  his  interest  in  the 
metal  which  Cronstedt  discovered  is  easily  understood  (131). 

In  1816  Hans  Peter  Eggertz,  Baron  Johan  Nordin,  and  J.  G.  Gahn 
founded  at  Falun  a  small  plant  for  the  manufacture  of  imitation  packfong 
from  the  nickeliferous  ores  of  the  Slattberg  and  Kuso  mines.  This  plant 
was  in  operation  until  1821,  when  it  was  destroyed  by  fire  ( 132 ) . 

Since  the  middle  of  the  seventeenth  century,  an  alloy  known  as  "white 
copper"  had  been  manufactured  at  Suhl  in  the  Thuringian  Forest  from 
old  slag  belonging  to  the  copper  smelters,  In  1823  it  was  found  to  contain 
copper  and  zinc.  The  manufacture  of  Argentans  or  Neusilber  ( German 
silver,  or  nickel  silver)  began  in  1824  (125,  126).  Until  1865  German 
silver  was  almost  the  only  form  in  which  nickel  was  used  commercially. 
The  first  pure  malleable  nickel  was  prepared  by  Joseph  Wharton  of 
Philadelphia  (125). 


168  DISCOVERY  OF  THE  ELEMENTS 

MANGANESE 

When  Cronstedt  died,  the  man  who  is  conceded  to  be  the  discoverer 
of  manganese  was  exactly  twenty  years  old.  Johan  Gottlieb  Gahn  was 
born  at  Voxna,  an  iron-mining  town  in  South  Helsingland  on  August  19, 
1745  (5).  Left  fatherless  at  an  early  age  and  obliged  to  earn  his  living 
in  the  mines,  he  shared  the  joys  and  sorrows  of  the  laborers  and  learned 
mining  "on  the  lowest  and  wettest  level"  (17).  He  studied  mineralogy 
under  Bergman,  became  expert  in  the  use  of  the  blowpipe,  and,  according 
to  Berzelius,  always  carried  it  with  him,  even  on  the  shortest  trips.  When 
Gahn  demonstrated  the  presence  of  copper  in  certain  kinds  of  paper  by 
burning  a  quarter  of  a  sheet,  heating  the  ash  with  the  blowpipe,  and 
displaying  a  tiny  speck  of  the  red  metal,  the  young  Berzelius  watched  him 
with  wonder  and  admiration  (11).  J,  Nickles  believed,  however,  that  this 
copper  must  have  been  volatilized  from  Gahn's  burner  ( 40 ) , 

Pyrolusite  has  been  used  for  centuries  in  the  manufacture  of  glass. 
After  mentioning  the  production  of  blue  glass  with  "zaffer"  ( a  mixture  of 
roasted  cobalt  ore  and  sand),  Vannoccio  Biringuccio  wrote  in  his  "Piro- 
technia"  in  1540,  "There  is  still  another  half  mineral  of  the  same  kind, 
so-called  Braunstein.  This  comes  from  Germany  and  is  found  especially 
in  Tuscany  in  Mt.  Viterbo  and  at  Salodiana  in  the  neighborhood  of  Monte- 
castello,  near  Cara.  It  is  dark  rust  brown.  It  does  not  melt  so  that  one 
can  obtain  metal  from  it.  But  when  one  adds  vitrifiable  substances  to  it, 
it  colors  them  a  handsome  violet.  The  master  glass-makers  color  their 
glasses  a  wonderful  violet  with  it.  The  master  potters  also  use  it  for  violet 
decorations.  Braunstein,  moreover,  when  mixed  with  molten  glass,  has 
the  special  property  of  purifying  it  and  making  it  white  instead  of  green  or 
yellow"  (57).  Because  of  the  last-named  property,  glassmakers  used  to 
call  it  sapo  vitri,  or  glass  soap. 

E  -F.  Geoffroy  said  that  "Magnesia  or  Manganesia  of  the  Glass- 
Makers,  the  Soap  of  Glass  of  Merret,  is  a  fossil,  metallick,  ferruginous 
Substance  resembling  Antimony  in  its  shining  Colour,  and  very  brittle. 
Pomet  mentions  two  Kinds  of  it,  one  ash-coloured,  which  is  not  easy  to 
be  got,  and  therefore  little  used;  the  other  black,  which  is  very  common. 
It  is  used  in  making  and  purifying  of  Glass;  for,  by  mixing  a  small  Quantity 
of  it  with  the  Glass,  whilst  in  Fusion,  it  clears  it  from  any  green  or  bluish 
Colours,  and  makes  it  more  transparent  and  bright;  and  it  was  on  that 
account  that  Merret  termed  it  Sapo  Vitri.  If  too  great  a  Quantity  of  it 
be  put  in,  it  gives  the  Glass  a  purple  Colour.  It  is  used  by  Potters  in 
colouring  their  Vessels  black,  as  the  Zaffera,  already  mentioned,  is  for 
blue.  The  same  Merret  says,  the  best  Manganese  is  that  which  is  hard, 
heavy,  sparkling,  and  blackish,  -and  which  being  reduced  to  Powder,  turns 


&OME  EIGHTEENTH-CENTURY   METALS 


169 


Lead  black.  It  is  dug  in  Germany,  Italy,  Piedmont,  and  in  England, 
near  the  Mendip  Hills  in  Somersetshire,  famous  for  Lead  Mines.  .  ." 
(133). 

The  Berlin  glass  and  porcelain  technologist  J,  H.  Pott  believed  that 
pyrolusite  consisted  of  phlogiston  and  an  earth  somewhat  like  that  in  alum 
(58).  In  1740  he  prepared  "chameleon  mineral"  (potassium  permanga 
nate)  and  other  compounds  from  it  and  showed  that  iron  is  not  a  constitu 
ent  of  pure  pyrolusite  (13). 

The  first  person  to  prepare  a  little  metallic  manganese  was  probably 
Ignatius  Gottfried  Kaim,  who  described  it  in  his  dissertation,  "De  metallis 
dubiis,"  which  was  published  at  Vienna  in  1770  (12).  Although  this  pub- 


Johan      Gottlieb      Gahn,      1745-1818, 

Swedish  chemist,  mineralogist,  and  min 
ing  engineer      Manufacturer  of  copper, 
sulfur,    sulfunc    acid,    and    red    ochre 
Discoverer  of  metallic  manganese 


lication  is  rare  and  inaccessible,  P.-J.  Macquer  left  an  abstract  of  it  in  his 
famous  chemical  dictionary.  By  heating  a  mixture  of  one  part  of  pulver 
ized  pyrolusite  with  two  parts  of  black  flux,  Kaim  obtained  a  bluish  white, 
brittle  metal  with  countless  shining  facets  of  different  shapes,  showing  in 
the  fracture  a  play  of  colors  from  blue  to  yellow.  He  claimed  that  this 
regulus  was  free  from  iron  (59).  This  incomplete  research  attracted  little 

notice. 

The  mineral  was  also  known  by  the  confusing  names  "black  mag 
nesia"  and  "manganese."  Torbern  Bergman  knew,  however,  that  it  was 
not  a  compound  of  the  alkaline  earth,  magnesia,  for  he  said,  "The  mineral 
called  black  magnesia  is  nothing  other  than  the  calx  of  a  new  metal,  which 


170  DISCOVERY  OF  THE  ELEMENTS 

must  not  be  confounded  with  lime  nor  with  magnesia  alba,"  He  failed, 
however,  in  all  attempts  to  reduce  the  ore  (13,  25),  and  finally  turned  the 
problem  over  to  his  friend  G.  W.  Scheele,  who  in  1774,  after  experimenting 
for  three  years,  presented  his  results  to  the  Stockholm  Academy  in  the 
form  of  a  paper  entitled,  "Concerning  manganese  and  its  properties."  In 
this  epoch-making  dissertation  he  announced  the  existence  of  the  gaseous 
element  chlorine  and  paved  the  way  for  the  discovery  of  oxygen  gas  and 
the  metals  barium  and  manganese.  Scheele  stated  that  the  mineral  known 
as  "manganese"  was  the  calx  of  the  metal  different  from  any  then  known 
(26). 

Although  Pott,  Bergman,  and  Scheele  all  believed  in  the  existence  of 
the  metal  manganese  none  of  them  were  able  to  isolate  it.  However,  in 
1774  Gahn  (25)  lined  a  crucible  with  moist  charcoal  dust,  placed  in  the 
center  a  mixture  of  the  pulverized  pyrolusite  and  oil,  and  covered  it  with 
more  of  the  charcoal  dust,  After  luting  another  crucible  to  this,  he  heated 
them  intensely  for  an  hour  and,  upon  opening  the  apparatus,  he  found  in 
it  a  button  of  metallic  manganese  weighing  about  a  third  as  much  as  the 
ore  from  which  he  had  isolated  it  (13,  30).  For  the  accomplishment  of 
this  difficult  reduction  and  for  the  isolation  of  this  important  metal,  Gahn 
deserves  high  praise. 

This  discovery,  like  most  of  his  others,  was  not  published  in  any 
scientific  journal  In  his  first  attempts,  Gahn  obtained  what  Scheele 
called  "reduced  pyrolusite  .  .  .  combined  with  much  phlogiston  and  a 
little  iron  "  On  May  16,  1774,  Scheele  sent  him  some  purified  pyrolusite 
with  the  suggestion,  "I  am  eagerly  waiting  to  see  what  kind  of  result  this 
pure  Braunstein  will  give  when  you  apply  your  hell-fire  to  it,  and  I  hope 
you  will  send  me  a  little  of  the  regulus  as  soon  as  possible"  (37).  On  June 
27th  of  the  same  year,  Scheele  thanked  Gahn  for  the  manganese  regulus 
["regulum  magnesiae"]  and  added,  "I  believe  that  the  Braunstein  regulus 
is  a  half  metal  different  from  other  half  metals  and  closely  related  to  iron" 

(37). 

In  his  notes  to  H.  T.  Scheffer  s  chemical  lectures,  which  were  pub 
lished  in  1775,  Torbern  Bergman  stated  that  a  fifteenth  metal  had  recently 
been  added  to  the  fourteen  which  Scheffer  had  discussed.  Because  of 
its  weight,  ability  to  color  glass,  and  its  precipitation  with  ferrocyanides 
(blodlut),'  Bergman  had  suspected  that  pyrolusite  must  contain  a  peculiar 
metal  as  an  essential  constituent,  "At  the  same  time/'  said  he,  THr.  J.  G. 
Gahn,  without  knowing  of  my  reasons,  actually  brought  forth  from  it  by 
reduction  a  half  metal  which  in  refractoriness  approaches  nearest  to 
platinum,  and  which,  moreover,  does  not  resemble  any  of  those  previously 
known.  .  .  .  Since  then,  I,  too,  have  obtained  the  regulus  of  pyrolusite  by 
reduction,  but  could  not  purify  it  from  iron"  (38). 


SOME  EIGHTEENTH-CENTUBY   METALS  171 

In  1785  P.  J,  Hjelm  published  in  the  Nya  Handlingar  of  the  Swedish 
Academy  of  Sciences  a  detailed  description  of  this  reduction.  He  obtained 
his  specimens  from  a  pyrolusite  quarry  in  Undenas  parish  in  Vermland. 
After  placing  a  mixture  of  a  known  weight  of  the  pulverized  sample  with 
a  little  oil  or  melted  tallow  and  powdered  coal  dust  or  blood  charcoal  in 
a  large  covered  crucible  lined  with  a  mixture  of  iron-free  clay  and  coal 
dust,  he  applied  sufficient  heat  from  his  forge  to  volatilize  the  oil  without 
allpwing  it  to  burst  into  flame.  In  less  than  an  hour,  he  obtained  a  regulus 
which  weighed  more  than  half  as  much  as  the  original  crude  pyrolusite. 
Assessor  Bengt  Qvist  suggested  to  him  that  the  metal  could  be  produced 
more  economically  in  a  cast  steel  furnace  or  wind  furnace  (60) . 

J.  C.  Ilsemann  of  Clausthal  also  obtained  manganese  independently 
without  previous  knowledge  of  the  methods  used  by  Gahn  and  Bergman. 
Ilsemann  reduced  110  pounds  of  pyrolusite  from  Ilsefeld  by  heating  it 
with  a  mixture  of  fluorspar,  lime,  powdered  charcoal,  and  ignited  salt,  and 
obtained  four  and  one-half  pounds  of  impure  metallic  manganese  from 
which  he  was  unable  to  separate  the  iron  (61). 

In  1784  Gahn  was  made  assessor  at  the  College  of  Mines;  he  also 
served  as  deputy  to  the  1819  Diet,  and  was  known  politically  as  a  Liberal 
(14).  He  was  not  only  a  brilliant  chemist  and  mineralogist  and  a  con 
scientious  public  official,  but  also  a  highly  successful  business  executive. 
He  owned  and  managed  mines  and  smelters,  and  introduced  new  indus 
trial  methods;  and  it  was  in  his  sulfuric  acid  plant  that  J,  J.  Berzelius  dis 
covered  the  element  selenium.  During  the  American  Revolution,  when 
large  amounts  of  pure  copper  were  needed  for  sheathing  ships,  Gahn's 
plant  at  Stora  Kopparberg  was  able  to  fill  large  rush  orders  (15).  It  is  a 
curious  fact  that  Assessor  Gahn  bore  such  a  striking  resemblance  in  fea 
tures,  gestures,  and  intellectual  interests  to  Dr,  William  Hyde  Wollaston, 
the  English  scientist  who  later  discovered  palladium  and  rhodium,  that 
he  was  often  called  "the  Wollaston  of  Stockholm"  (16).  Berzelius  once 
stated,  in  fact,  that  one  "would  take  them  for  sons  of  the  same  father" 
(16).  Thomas  Thomson,  who  once  visited  Assessor  Gahn  at  his  home  in 
Falun,  said  that  "his  manners  were  the  most  simple,  unaffected  and  pleas 
ing  of  'all  the  men  of  science"  he  had  ever  met,  and  that  "benevolence  and 
goodness  of  heart  .  .  .  beamed  in  his  countenance/' 

When  Edward  Daniel  Clarke  visited  Falun,  he  said  that  "perhaps  in 
no  part  of  the  world"  will  the  traveler  "meet  with  superintendents  so  well 
informed  ...  at  the  head  of  whom  is  the  celebrated  Gahn,  whose  acquire 
ments,  and  the  kindness  he  has  always  shewn  to  strangers,  have  entitled 
him  to  respect  and  consideration  in  all  the  Academical  Institutions  of 

Europe Hospitality  in  a  Swede  is  what  we  may  always  expect;  but 

the  attention  paid  to  strangers  by  Mr.  Gahn,  especially  if  their  visits  had 


172  DISCOVERY  OF  THE  ELEMENTS 

any  view  to  science,  was  of  a  more  exalted  nature,  He  not  only  shewed 
a  zeal,  as  if  actuated  by  a  religious  duty,  to  satisfy  scientific  inquiries;  but 
he  did  more-he  directed  them;  and  himself  endeavoured  to  stimulate 
the  ardour  of  those  with  whom  he  conversed  ...  by  exciting  and  then 
gratifying  their  curiosity"  (55). 

At  the  time  of  his  sixty-eighth  birthday,  Gahn  received  a  novel  con 
gratulatory  note  from  Berzelius,  which  read:  "From  Her*  Assessor's  last 
letter  I  was  happy  to  Bnd  new  support  for  the  doctrine  of  definite  propor 
tions.  Heir  Assessor  was  68  on  August  19;  the  following  day  (the  20th) 
I  became  34;  now  34X2— 68,  from  whence  it  follows  that  Herr  Assessor 
is  equal  to  a  multiple  of  me  by  two  ..."  (56). 

Gahn,  unfortunately,  left  most  of  his  scientific  work  unpublished, 
leaving  only  a  few  papers  on  the  blowpipe,  on  a  sensitive  balance,  and  on 
economy  in  the  operation  of  smelters.  He  died  in  Stockholm  on  December 
8,  1818,  at  the  age  of  seventy-three  years.  In  a  biographical  sketch  in 
the  Annals  of  Philosophtj,  one  may  read  this  high  tribute: 

To  sum  up  the  whole,  we  may  safely  say  that  he  was  alike  eminent  as  a 
practical  chemist  and  mechanic,  as  a  patriot  in  public,  and  a  friend  in  private 
life,  as  presiding  over  the  interests  of  the  miner  and  of  the  farmer,  and  in  fine  as 
the' guardian  and  overseer  of  the  large  family  of  his  native  poor  *  It  will  not 
indeed  be  easy  to  find  another  whose  talents  have  been  at  once  more  biilhant 
and  more  useful,  who  has  been  more  admired  and  more  loved  by  his  country, 
than  John  Gottlieb  Gahn  (15). 

Manganese  in  Iron  Ores.  In  1773  Sven  Rinman  had  the  iron  ores 
at  Dingelvik  in  Dalsland  tested  for  manganese  (89).  In  the  following 
year  P,  J.  Hjelm  defended  a  thesis,  under  Torbern  Bergman,  in  which 
he  showed  that  manganese  is  a  common  constituent  of  bog  iron  ores, 
magnetite,  and  bloodstone  (hematite),  "On  accurate  investigation," 
said  he,  "of  several  substances  found  on  trips  through  the  mining  re 
gions,  Braunstein  (pyrolusite)  occurred  as  a  rather  common  accompani 
ment  When  earths,  slags,  pig  iron,  etc.  were  investigated  and  waters 
tested,  I  found  traces  of  it  everywhere"  (134).  In  the  opinion  of  A.  E. 
Nordenskiold,  Hjelm  may  therefore  be  credited  with  the  discovery  of 
the  wide  distribution  of  manganese  in  nature  and  the  observation  that 
pig  iron  made  from  manganiferous  iron  ores  often  produces  excellent 
steel  (89). 

Chameleon  Mineral  (Potassium  Permanganate).  J.  R.  Glauber  men 
tioned  in  1659,  in  his  "Teutschlands  Wohlfarth,"  that  when  pyrolusite  is 

*  Assessor  Gahn  helped  to  establish  the  first  poorhouse  at  Falun. 


SOME  EIGHTEENTH-CENTURY   METALS  173 

fused  with  caustic  potash  and  the  mass  is  dissolved  in  water,  the  solution 
is  at  first  purple  but  changes  through  blue  and  red  to  green,  J.  H.  Pott 
stated,  however,  in  1740,  in  his  research  on  pyrolusite,  that  a  solution 
obtained  in  this  manner  is  green  at  first  and  that  it  becomes  blue,  then 
red,  and  finally  green  again  (134).  In  1774,  C,  W.  Scheele  expressed 
the  view  that  the  solution  of  pyrolusite  in  potash  was  actually  blue  but 
that  it  could  be  colored  red  by  suspended  particles  of  pyrolusite  or 
green  by  fine  particles  of  yellow  iron  oxide  (135), 

Even  at  the  beginning  of  the  nineteenth  century,  chemists  still  dis 
agreed  as  to  the  cause  of  these  remarkable  color  changes.  Christian 
Friedrich  Bucholtz  (1770-1818),  a  nephew  of  W.  H.  S.  Bucholtz,  stated 
in  1809  that  the  green  solution  became  red  because  it  absorbed  oxygen 
from  the  atmosphere  (134,  136).  His  scientific  career  was  cut  short 
by  prolonged  illness,  loss  of  vision,  and  premature  death  ( 137) . 

M.-E.  Chevreul  believed  that  the  green  and  red  "chameleons"  were 
in  the  same  stage  of  oxidation  and  that  they  were  more  highly  oxidized 
than  the  colorless  salts  of  manganese  (138).  By  mixing  the  green  and 
red  solutions  in  different  proportions,  he  produced  all  the  intermediate 
shades  through  green,  blue,  indigo,  purple,  and  red. 

Pierre-Frangois  CheviUot  and  William  Frederic  Edwards  found  in 
1817  that  when  they  fused  pyrolusite  in  caustic  potash  out  of  contact 
with  air,  they  obtained  no  chameleon  mineral.  They  also  found  that 
the  change  to  the  red  form  took  place  faster  in  pure  oxygen  than  in  the 
atmosphere,  and  that  when  the  pyrolusite  was  in  excess  in  the  fusion 
mixture,  they  obtained  the  red  form  directly.  They  concluded  therefore 
that  the  green  solution  of  the  chameleon  mineral  contained  more  potash 
than  the  red  one.  In  1818  they  prepared  similar  compounds  of  sodium, 
barium,  and  strontium  (139).  In  1820  J.  G.  Forchhammer  of  Copen 
hagen,  in  his  doctor's  dissertation,  distinguished  two  different  acids 
(manganic  in  the  green  solution  and  permanganic  in  the  red  one),  and  in 
1830-32  Eilhard  Mitscherlich  determined  the  chemical  composition  of 
these  acids  (140, 141, 150). 

Manganese  in  Plants.  When  Scheele  warmed  some  sifted  vegetable 
ashes  with  spirit  of  salt  (hydrochloric  acid)  in  1774,  he  noticed  an  odor  of 
aqua  regia  like  that  obtained  when  pyrolusite  is  similarly  treated.  On 
investigating  the  cause  of  this  odor,  he  found  that  the  ash  contained 
"manganese"  (manganese  dioxide).  "Nevertheless,"  said  Scheele,  "I 
observed  very  little  in  the  ashes  from  Serpillum:  wood  ashes  gave  more 
of  it"  (142,  147). 

In  a  letter  to  Gahn  on  March  28,  1774,  he  wrote:  "I  have  also 
discovered  some  of  this  earth  [baryta]  as  well  as  a  little  Braunstein 


174  DISCOVERY  OF  THE  ELEMENTS 

[manganese  dioxide]  in  vegetable  ash,  and  am  delighted  that  I  have 
conclusively  found  in  the  presence  of  Braunstein  the  reason  why  alkalia 
fixa  assumes  a  blue-green  color  on  calcination"  (143). 

L.-J.  Proust  detected  manganese  in  the  ash  of  the  pine,  the  fig  tree, 
the  calendula,  and  other  plants  (144).  In  1849  Prince  Salm-Horstmar 
found  it  in  the  ash  of  the  oat  plant  (45).  According  to  A.  T.  Shohl,  plants 
store  manganese  in  their  leaves  and  seeds,  and  use  it  as  an  essential 
element  in  their  nutrition  (146). 

Manganese  in  Animals.  In  1808  A.-F.  de  Fourcroy  and  N.-L.  Vau- 
quelin  detected  manganese  in  the  bones  of  the  ox,  and  three  years  later 
they  demonstrated  its  piesence  in  human  bones  (148).  In  1830  Ferdi 
nand  Wurzer  of  Marburg  detected  a  small  amount  of  manganese  in 
human  blood  and  published  his  results  in  PoggendorfFs  Annalen  and  in 
Schweigger's  Journal  (149).  E,  R,  Orent  and  E.  V,  McCollum  proved 
that  manganese  is  an  essential  element  in  animal  nutrition  ( 146 ) . 


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(114)  WINDERLICH,   RUDOLF,   "Chemische   Kenntnisse   der   alt  en   Babylonier  und 

Agypter,"  Aus  der  Heimat,  47,  116-21  (Apr.,  1934) 

(115)  WINDERLICH,   RUDOLF,    "A  Persian   description  of  the   faience   technic   at 

Kashan  in  1301  AD.,"  /  Chem.  Educ ,  13,  361-2  (Aug,  1936);  RITTER, 
H.,  J.  RUSKA,  F  SARRE,  and  R.  WINDERLICH,  "Orientalische  Steinbucher 
und  persische  Fayence-Techmk,"  German  Archaeological  Institute,  Istan 
bul,  1935,  70  pp. 

(116)  MARGGRAF,  A.  S  ,  "Chymische  Schriften,"  Ref.  (53),  Vol   1,  pp    133-4, 

(117)  POMET,  PIERRE,  "The  History  of  Drugs,"  3rd  ed.,  J.  Bonwicke  et  al.,  London, 

1737,  p.  368. 

(US)  BRANDT,  GEORG,  "Untersuchung  und  Beschreibung  erner  neuen  Art  des 
Kobaltes,"  Crell's  Neues  chem.  Archiv,  3,  221-30  (1785),  ibid.9  5,  45-8 
(1786);  Acta  Societ  Regiae  Sc.  Upsal,  arm.  1742,  Stockholm,  1748;  Vet. 
Acad.  HandL,  8,  127  (1746).  Published  in  1752 j  "Recueil  des  memoires 
.  .  .  contenus  dans  les  Actes  de  TAcad  Roy.  des  Sciences  de  Stockolm 
[sic],"  Vol.  1,  P.-F.  Didot  le  Jeune,  Paris,  1764,  pp  38-50. 

(119)     BECKMANN,  JOHANN,  Ref.  (47),  Vol.  1,  pp.  109-10,  131-2,  478-87. 


180  DISCOVEBY  OF  THE  ELEMENTS 

(120)     KOPP,  HERMANN,  Ref.  (19),  Vol.  4,  pp.  155-7 

(131)     "Cobalt  m  meteorites/'  Quarterly  J  Sci ,  6,  162  (1819).  ^ 

(122)  STROMEYER,  F.,  "Decouverte  du  cobalt  dans  le  fer  meteoiique,    Ann   chim. 

phys.,  (2),  8,98-9(1818)  _ 

(123)  FORCHHAMMER,  J.  G,  "On  the  composition  of  sea  water  m  the  different 

parts  of  the  ocean,"  Phil  Trans,,  155,  203-62  ( 1865) . 

(124}     SCHULTZE,  M.  O.,  "Metallic  elements  and  blood  formation,"  Physiol.  Rev., 
20,  37-67  (Jan.,  1940).  XT 

(125)  STANLEY,  R.  C.,  "Nickel.     Past  and  Present,"  International  Nickel  Go.  of 

Canada,  1934,  pp.  11-22. 

(126)  KOPP,  HERMANN,  Ref    (19),  part  4,  pp.  157-9. 

(127)  "Account  of  a  memoir  of  M.  Proust,"  Nicholsons  } ,  4,  356-7  (Nov  ,  1800). 

(128)  MERRILL,  G.  P.  and  W.  F   FOSHAG,  "Minerals  from  Earth  and  Sky,"  Vol.  3, 

Smithsonian  Scientific  Series,  Washington,  D,  C.,  1929,  p.  101. 

(129)  "Nickel  at  the  Vienna  Exposition/'  Am.  Chemist,  5,  181  (Nov,  1874). 

(130)  ENGESI-ROM,  GUSTAF  VON,  "Pak-fong,  em  chmesisches  weisses  Metall,"  Crell's 

Neuevte  Entdeckungen,  3,  178-81  (1781),  Vet  Acad   Handl ,  37,  35-8. 

(131)  ZENZEN,  "Om  den  Swedenborgsstammen  och  det  Swedenborgska  marnior- 

bordet/'  Svenska  Linne-Sallskapets  Arsskrift,  14,  95-9  (1931). 

(132)  EGGERTZ,  V ,  "Hans  Peter  Eggertz,  Lefnadsteckningar  ofver  K.  Svenska  Vet- 

enskaps   Akademiens    efter   ar    1854    afhdna   ledamotei,"    Vol     2,    Stock 
holm,  1878-85,  pp  37-41. 

(133)  GEOFFROY,  E.-F  ,  Ref,  (93),  pp.  178-9. 

( 134 )  HJELM,  P,  J  ,  "Versuch  uber  die  Gegenwart  des  Braunstems  m  den  Eisen- 

erzen,"    Crell's   Neueste   Entdeckungen,    6,    164-71    (1782),    Vet.   Acad 
Handl,  39,8^-7  (1778). 

(135)  DOBBIN,  LEONAHD,  "The  Collected  Papers  of  G.  W.  Scheele,"  G.  Bell  and 

Sons,  London,  1931,  p.  38, 

(136)  "Death   of  G    F.   Bucholtz,   1770-1818,"   Schweiggers  Neues  Journal  fw 

Chemie  und  Physik,  (4),  22,  131-2  (1818). 

(137)  THOMSON,  THOMAS,  "Death  of  C.  F.  Bucholtz,"  Annals  of  Philos.,  13?  72r-3 

(Jan.,  1819). 

(138)  CHEVREUL,    M.-E ,   "Note  sur  la   cause  des   changemens   de   couleur  ^que 

presents  le  cameleon  mineral,  extraite  d'un  travail  sur  le  manganese," 
Ann  Chim  Phys ,  (2),  4,  42-9  (1817). 

(139)  CEffivnxoT  and  EDWABDS,  "Me*moire  sur  le  cameleon  mineral/'  Ibid ,   (2), 

4,  287-97  (1817);  Ibid,  (2),  8,  337-58  (1818). 

(140)  KOPP,  HERMANN,  Ref.  (19),  Part  4,  pp  88-9. 

(141)  MITSCHERLICH,  E,   "Ueber  die   Mangansaure,   Uebermangansaure,    Ueber- 

chlorsaure,  und  die  Salze  dieser  Sauren,"  Ann,,  2,  5-11  (1832). 

(142)  DOBBIN,  LEONABD,  Ref.  (135),  pp,  3-16,  46-7,  209-14,  295-304;  SCHEELE, 

Vet.  Acad.  Handl,  32,  120-38  (1771);  Ibid.,  35,  89-116,  177-94  (1774), 
SCHEELE,  Vet  Acad.  Nya  Handl,  1,  18-26  (1780),  Crell's  Ann.,  5,  3-17 
(1786). 

(143)  NORDENSKIOLD,  A   E ,  Ref    (30),  pp.  118,  324-5,  399.     Letters  of  Scheele 

to  Gahn,  Bergman,  and  Hjelm 

(144)  THOMSON,  THOMAS,  "A  System  of  Chemistry/'  2nd  ed.,  Vol.  4,  Bell  and 

Bradfute  et  al,  Edinburgh,  1804,  p   357, 

(145)  FISHER,  E    A.,  "Manganese  as  a  fertilizer/1  Chem    World,  3,  319   (Dec., 

1914),  SALM-HORSTMAR,  J.  Prakt.  Chem,  46-7,  193  (1849) 

(146)  SHOHL,  A.  T.}  Kef    (113),  pp.  243-5. 

(147)  KOPP,  HERMANN,  Ref.  (19),  Vol.  3,  pp.  345-71;  VoL  4,  pp   82-9. 

(14S)  FOUHCROY,  A.-F.  DE  and  N.-L.  VAUQUELIN,  "Experiments  on  human  bones, 
as  a  supplement  to  the  paper  on  the  bones  of  the  ox,"  Nicholson's  J,,  (2), 
30,  256-60  (Dec.,  1811). 


SOME    EIGHTEENTH-CENTURY    METALS  181 

(149)  "Manganese  in  human  blood,"  PM   Mag.,  (2),  9,  390  (May,  1831). 

(150)  PETERS,   KARL,   "Eilhard  Mitscherkch  und   sem  Geschlecht,"  Verlag   C.   L. 

Mettcker  &  Sohne,  Jever,  1951,  31  pp 

(157)  PROVENZAL,  GIULIO,  "Profili  Bio-Bibliografici  di  Chimici  Italian!  Sec.  XV- 
Sec.  XIX,"  Istituto  Nazionale  Medico  Farmacologico  "Serono,"  Rome, 
1937,  pp.  5-8. 

(152)  MORLEY,  HENRY,  "Palissy  the  Potter/'  New  ed,   (not  dated),  Cassell  Petter 

&  Galpm,  London,  Paris,  and  New  York,  320  pp, 

(153)  BRAUN,  A.,  Phil   Mag,  (4),  8,  156  (1854) 

(154)  RAULIN,  /,  Ann.  Sci.  Mat.,  (5),  2,  224  (1869). 


Published  by  permission  of  the 
Royal  College  of  Physicians 

William  Prout,  1785-1850.  English  physician,  physiologist,  and  chemist. 
He  proved  that  the  acidity  of  the  gastric  juice  is  due  to  hydrochloric  acid; 
showed  that  the  molecular  weight  o£  any  substance  is  equal  to  twice  its 
vapor  density  referred  to  hydrogen;  and  put  forth  the  hypothesis  that  the 
atomic  weights  of  all  of  the  elements,  referred  to  hydrogen  as  unity,  are 

integers.     See  ref.    (54). 


Ceux  qui  veulent  aujourd'hui  faire  passer  la  Chymie 
pour  tine  science  nouvelle  montrent  le  peu  de  con- 
noissance  quils  out  de  la  nature  &  de  la  lecture  des 
Anciens  (51).  Those  who  try  today  to  pass  chemistry 
off  as  a  new  science  show  how  little  knowledge  they 
have  of  the  character  and  literature  of  the  ancients. 


6 


Old  compounds  of  hydrogen  and  nitrogen 


A 

-/JLlthough  hydrogen  gas  has  been  known  only  since  the  seven 
teenth  century,  many  of  its  compounds  have  been  recognized  since  much 
more  ancient  times.  Hydrogen  is  found  everywhere  in  nature,  combined 
in  the  forms  of  water,  acids,  alkalies,  organic  compounds,  hydrogen 
sulfide,  petroleum,  natural  gas,  marsh  gas,  asphalt,  and  coal,  as  an  essential 
constituent  of  all  living  beings,  and  as  water  of  hydration  or  as  hydroxyl 
in  many  minerals,  Long  before  the  element  nitrogen  (nitrogen  gas)  was 
discovered,  compounds  such  as  sal  ammoniac,  nitric  acid,  and  saltpeter 
were  well  known. 


HYDROGEN  COMPOUNDS 

Vinegar  and  Pyroligneous  Add.  Vinegar  (acetic  acid)  is  mentioned 
several  times  in  the  Bible,  as,  for  example,  in  Proverbs  10,  26:  "As  vinegar 
to  the  teeth  and  as  smoke  to  the  eyes,  so  is  the  sluggard  to  them  that 
send  him,"  It  was  known  to  Theophrastus  three  centuries  before  the 
birth  of  Christ,  and  was  used  in  the  manufacture  of  white  lead  and 
verdigris  and  in  extracting  mercury  from  cinnabar  (I). 

In  the  seventeenth  century  J,  R.  Glauber,  in  his  "Description  of 
New  Philosophical  Furnaces,"  told  in  detail  "how  an  acid  spirit,  or 
vinegar,  may  be  distilled  out  of  all  vegetables,  as  hearbs,  woods,  roots, 
seeds,  etc/'  (2).  "Now  this  spirit,"  said  he,  "(being  rectified)  may 
commodiously  be  used  in  divers  Chymical  operations,  for  it  doth  easily 
dissolve  animal  stones,  as  the  eyes  of  Crabs,  the  stones  of  Perches  and 
Carps,  Corals  also  and  Pearls,  etc.  as  doth  vinegar  of  wine.  By  means 
thereof  are  dissolved  the  glasses  of  metals,  as  of  tin,  lead,  antimony, 
and  are  extracted  and  reduced  into  sweet  oyles,"  Glauber  s  "vinegar  of 
woods"  is  now  known  as  pyroligneous  acid. 

Johann  Rudolf  Glauber  was  born  in  1604,  the  son  of  a  barber-surgeon 
in  Karlstadt,  Franconia.  In  his  youth  he  earned  his  living  at  Vienna  by 
making  mirrors,  At  the  age  of  twenty-one  years  he  discovered  the 
medicinal  value  of  sodium  sulfate,  which  has  since  been  known  as 
Glaubers  salt.  Later,  in  Amsterdam,  he  bought  a  large  house  which 

183 


184  DISCOVERY   OF  THE  ELEMENTS 

had  formerly  belonged  to  an  alchemist,  and  converted  it  into  a  fine 
laboratory  equipped  with  furnaces  and  apparatus  of  his  own  design.  The 
German  edition  of  his  "New  Philosophical  Fmnaces"  was  published  in 
Amsterdam  during  the  years  1648  to  1650,  and  in  1651  English  and  Latin 
editions  appeared  (52). 

At  about  the  same  time  Glauber  established  wine  presses  at  Weit- 
heim  and  Kitzingen.  An  admirer  who  translated  Glauber's  "Fiuni  Novi 
Philosophici"  into  English  said  in  his  preface:  "I  therefore  piesent  you 
with  a  rich  Cabinet  of  nature's  unvaluable  Jewels;  But  know,  that  it  hath 
many  doors,  the  one  whereof  as  being  shut  to  many,  but  not  to  all,  1  have 
opened  with  an  English  key  ..."  (2).  Glauber,  he  said,  "is  canyed 
upon  the  wings  of  Fame  throughout  the  whole  woild,  His  Fame  all 
know  is  great,  and  flyes  high,  but  his  worth  sm mounts  his  Fame.  He 
is  a  Philosopher  and  Chymist  indeed"  (2). 

In  1655  or  1656  Glauber  returned  to  Amsterdam,  where  Samuel 
Sorbiere  visited  him  in  1660.  Glauber  was  living  in  a  mansion  with  four 
large,  magnificent  laboratories  at  the  rear,  where  five  or  six  men.  were 
employed,  A  progressive  illness,  which  may  have  been  caused  by  pro 
longed  study  of  poisonous  compounds,  brought  Glauber's  life  to  a  close 
in  1670  (53). 

J.  G.  Gahn  of  Falun,  Sweden,  was  a  manufacturer  of  vinegar,  and  in 
1816  J.  J,  Berzelius  entered  into  partnership  with  him  and  with  H.  P. 
Eggertz  in  the  manufacture  of  sulfuric  and  nitric  acids,  white  lead  and 
pigments,  soft  soap,  mustard,  and  vinegar  at  Gripsholm  (3)  When 
Gahn  was  perfecting  his  process  for  the  manufacture  of  vinegar  he 
received  valuable  help  from  his  wife.  In  a  letter  to  Berzelius  on  Febru 
ary  19,  1804  he  wrote:  "I  congratulate  you  on  your  success  in  making 
vinegar.  My  wife,  who  is  always  dabbling  in  vinegar-making  for  the 
household,  has  always  made  the  same  observation,  as  Herr  Doctor  in 
regard  to  the  difference  between  wooden  and  large  stone  containers: 
always  quicker  and  stronger  vinegar  in  the  latter/*  One  of  the  ingredi 
ents  of  Fru  Gahn's  vinegar  was  a  herring  (4). 

Aqua  Tortis  (Nitric  Acid).  The  preparation  of  nitric  acid,  or 
aqua  fortis,  was  described  in  the  Latin  treatise  "De  invenfaone  veritatis," 
of  the  13th-  or  14th-century  alchemist  Pseudo-Geber  (5).  From  the 
thirteenth  to  the  sixteenth  centuries,  Oriental  chemists  prepared  it  by 
distilling  a  mixture  of  copper  vitriol,  saltpeter,  and  alum  (6).  Raimundo 
Lulio  (Raymond  Lully,  1235-1315)  substituted  cinnabar  for  the  alum. 
Albert  the  Great,  Georgms  Agricola,  J.  R.  Glauber,  and  the  author  of 
the  writings  attributed  to  "Basil  Valentine"  also  described  the  prepara 
tion  of  this  acid.  Because  of  the  danger  involved  in  its  preparation,  it 
had  only  limited  application  until,  in  the  sixteenth  century,  there  arose 


OLD  COMPOUNDS   OF  HYDROGEN   AND   NITROGEN  185 

great  demand  for  it  for  the  parting  of  gold  and  silver  (6).  In  the  eight 
eenth  century,  an  improved  process  of  manufacturing  sulfuric  acid  by 
the  oxidation  of  sulfur  with  saltpeter  greatly  lowered  the  price  of  oil 
of  vitriol  (sulfuric  acid),  and  in  turn  made  possible  the  manufacture  of 
nitric  acid  directly  from  saltpeter  and  sulfuric  acid  (7). 

Because  of  its  relation  to  saltpeter,  P.-J,  Macquer  regarded  nitric 
acid  as  a  kind  of  sulfuric  acid  modified  by  its  passage  through  animal  and 
vegetable  substances.  "In  1750,"  said  he,  "the  Royal  Academy  of  Sciences 
at  Berlin  proposed  an  account  of  the  generation  of  Nitre  as  the  subject 
for  their  prize,  which  was  conferred  on  a  Memoir  wherein  this  last 
opinion  was  supported  by  some  new  and  very  judicious  experiments" 
(8).  Macquer  stated  that  "the  Nitrous  [nitric]  Acid  is  never  found 
but  in  earths  and  stones  which  have  been  impregnated  with  matters 
subject  to  putrefaction  .  ."(8). 

Oil  of  Vitriol  (Sulfuric  Acid).  Geber,  Vincent  de  Beauvais  (who 
wrote  the  "Speculum  naturale"  in  the  middle  of  the  thirteenth  century), 
and  Albert  the  Great  all  mentioned  a  "spirit"  which  could  be  prepared  by 
strongly  heating  alum  (9).  This  must  have  been  sulfuric  acid.  The 
unknown  author  of  the  works  of  "Basil  Valentine"  gave  detailed  de 
scriptions  of  the  preparation  of  this  acid  by  two  methods:  first,  by  dis 
tillation  of  calcined  iron  vitriol  and,  second,  by  heating  a  mixture  of 
stibnite  (antimonious  sulfide),  sulfur,  and  nitric  acid  (aqua  fortis). 
The  former  process  yielded  a  fuming  sulfuric  acid  containing  excess 
sulfur  trioxide.  In  his  "Alchymia/'  Andreas  Libavius  (Liebau)  showed 
in  1595  that  the  acids  prepared  from  green  vitriol,  blue  vitriol,  and 
sulfur  are  identical  (9). 

The  first  industrial  preparation  of  sulfuric  acid  from  green  vitriol 
(ferrous  sulfate),  according  to  Hermann  Kopp,  was  by  Johann  Christian 
Bernhardt  in  1755  (9, 10).  A  fuming  sulfuric  acid  known  as  Nordhausen 
oil  of  vitriol  was  manufactured  at  Nordhausen,  Thuringia,  from  partially 
dehydrated  green  vitriol  (II). 

The  manufacture  of  sulfuric  acid  by  burning  sulfur  with  saltpeter 
was  a  British  discovery  "English  artisans,"  said  Guyton  de  Morveau 
in  the  "Encyclopedic  Methodique,"  "have  been  credited  with  the  inven 
tion  of  this  method,  and  far  be  it  from  me  to  dispute  it;  only  those  who 
have  never  actually  engaged  in  it  are  unaware  that  it  is  also  an  invention 
to  adapt  to  a  large-scale  factory  manipulations  whose  principle  formerly 
existed  in  books;  but  it  is  also  fair  to  make  known  how  near  theory  itself 
had  come  to  this  accomplishment  [Louis]  L&nery  had  already  taught 
that  one  could  extract  vitriolic  acid  from  sulfur  by  mixing  it  with  Vie  of 
its  weight  of  niter  or  saltpeter,  and  detonating  this  mixture  with  a  hot 
iron  in  the  center  of  a  large  stoneware  vessel  at  the  bottom  of  which 


186  DISCOVERY   OF  THE  ELEMENTS 

water  had  been  placed,  the  liquid,  filtered  and  concentrated  by  evapo 
ration,  bore  the  name  of  oil  of  sulfur'  (11). 

Hermann  Kopp  found  the  earliest  mention  of  the  British  process  in 
Robeit  Dossie's  "Elaboratory  laid  open"  in  1758.  Dossie  spoke  only  of 
glass  receptacles  for  the  acid  (9).  In  his  "Institutes  of  Experimental 
Chemistry"  in  the  following  year,  he  stated  that  this  process  had  greatly 
lowered  the  price  of  oil  of  vitriol  and  had  made  possible  the  use  of  this 
acid  in  the  preparation  of  aqua  foitis  (nitric  acid)  from  saltpeter  (7). 

In  1746  Dr.  John  Roebuck  (1718-1794),  of  Birmingham,  and  Samuel 
Garbett  substituted  lead  chambers,  each  about  six  feet  square,  for  the 
glass  globes  introduced  six  years  previously  by  Joshua  Ward  (22),  an 
improvement  which  cut  down  the  cost  of  producing  the  acid  to  one- 
fourth  of  its  former  amount  (12,  13).  Three  years  later,  after  the 
substitution  of  sulfuric  acid  for  sour  milk  in  the  old  process  of  bleaching 
had  created  a  demand  for  the  acid,  Roebuck  and  Garbett  erected  a 
sulfuric  acid  plant  at  Prestonpans,  on  the  east  coast  of  Scotland  (14). 
Since  a  salt  industry  also  flourished  there,  Prestonpans  was  named  for 
the  salt  pans. 

When  Berzelius  visited  Paris  in  1818,  he  inspected  a  lead-chamber 
plant  in  which  sulfuric  acid  was  made  by  burning  sulfur  with  saltpeter, 
the  daily  output  being  300  pounds.  The  acid  was  condensed  first  in 
a  lead  caldron  and  then  in  a  platinum  boiler.  This  plant  had  three  pairs 
of  lead  chambers  and  two  small  platinum  kettles,  each  of  which  had  a 
capacity  of  from  2  to  2l/2  gallons.  The  cost  of  the  two  platinum  kettles 
was  9000  francs  (15). 

Aqua  Regia.  Geber  described  the  preparation  of  nitric  acid  (aqua 
fortis)  in  his  "De  inventione  veritatis,"  and  added  that,  if  one  adds  sal 
ammoniac  to  this  acid  it  becomes  a  more  powerful  solvent  (5,  16). 
Raymond  Lully  (Raimundo  Lulio)  and  Albert  the  Great  (St.  Albert) 
prepared  it  in  the  same  way.  By  the  time  the  writings  attributed  to 
"Basil  Valentine"  were  published,  hydrochloric  acid  (acid  of  salt)  was 
known,  this  work  describes  the  preparation  of  aqua  regia  by  mixing 
three  parts  of  hydrochloric  acid  with  one  part  of  nitric  acid  (16, 17) .  J.  R. 
Glauber  prepared  it  from  common  salt  and  nitric  acid  and  from  saltpeter 
and  hydrochloric  acid  (18). 

Hydrochloric  Acid  ("Acid  of  Salt")  .  Although  hydrochloric  acid 
was  well  known  to  Libavius  in  1595,  J.  R,  Glauber  stated  in  the  middle 
of  the  following  century  that  it  was  the  most  expensive  and  most  diffi 
cult  to  prepare  of  all  the  acids  (16).  In  his  "Description  of  the  New 
Philosophical  Furnaces,"  Glauber  gave  the  following  method  for  pre 
paring  "spirit  of  salt":  "Mix  salt  and  vitrial  or  allome  [vitriol  or  alum] 
together,  grinding  them  very  well  in  a  mortar.  .  .  .  Then  cast  this 


OLD   COMPOUNDS   OF  HYDROGEN  AND   NITROGEN  187 

mixture  into  the  fire  with  an  Iron  ladle,  viz.,  so  much  of  it  as  will  he 
sufficient  to  cover  the  coals,  and  then  with  a  great  fire  the  spirits  come 
forth  into  the  receivers.  .  .  .  There  can  by  this  way  distill  no  spirit  of 
vitriol  or  allome  .  .  .  the  reason  of  this  is  because  these  spirits  are  far 
more  heavy  than  the  spirit  of  salt,  neither  can  they  ascend  so  great  a 
height  .  .  .  because  in  this  furnace  the  spirit  of  allome  and  vitriol  [sul- 
furic  acid]  cannot  be  made  unless  a  pipe  go  out  of  the  furnace  near  the 
grate."  Glauber  stated  that  his  spirit  of  salt  "dissolveth  all  metals  and 
minerals  (excepting  silver)"  (2). 

P.-J.  Macquer  (1718-1784)  said  in  his  "Elements  of  the  Theory 
and  Practice  of  Chymistry"  that  "the  Acid  of  Sea-Salt  is  so  called  be 
cause  it  is  in  fact  obtained  from  such  Sea-Salt  as  we  use  in  our  kitchens 
It  is  not  certainly  known  in  what  this  Acid  differs  from  the  vitriolic 
and  the  nitrous  [sulfuric  and  nitric],  with  regard  to  its  constituent 
parts"  (S). 

Free  Hydrochloric  Acid  in  the  Stomach.  On  December  23,  1823,  Dr 
William  Prout  (1785-1850)  discovered  the  existence  of  free  hydro 
chloric  acid  in  the  stomach.  In  the  Quarterly  Journal  of  Science  and 
the  Arts  for  1824  one  may  read:  "The  following  are  the  proofs  of  the 
existence  of  free  muriatic  [hydrichloiic]  acid  which  Dr.  Prout  has 
laid  before  the  Royal  Society,  The  contents  of  a  stomach  having  been 
digested  in  distilled  water,  the  solution  obtained  was  divided  into  four 
equal  parts.  One  of  these,  evaporated  to  dryness,  burnt,  and  examined 
in  the  usual  way,  gave  the  quantity  of  muriatic  acid  in  combination 
with  fixed  bases.  A  second,  being  previously  saturated  with  an  alkali, 
was  treated  in  a  similar  way,  and  gave  the  whole  quantity  of  muriatic 
acid  in  the  stomach.  A  third,  carefully  neutralized  with  a  known  solu 
tion  of  alkali,  gave  the  quantity  of  free  acid.  The  fourth  was  reserved 
for  any  required  experiment.  In  this  way  Dr.  Prout  ascertained  that 
the  unsaturated  muriatic  acid  in  the  stomach  was  always  consider 
able  .  .  ."(19,55). 

Hydrogen  in  Plants  and  Animals  J.-B.  Boussingault  showed  that 
plants  can  decompose  water,  liberating  oxygen  and  fixing  the  hydrogen, 
and  that  they  are  thus  able  to  build  up  oils  and  waxes  high  in  hydro 
gen  (20).  With  J.-B.  Dumas  he  pointed  out  that  "if  the  animal  realm 
constitutes  an  immense  apparatus  for  combustion,  the  vegetable  kingdom, 
on  the  other  hand,  constitutes  an  immense  apparatus  for  reduction,  in 
which  reduced  carbonic  acid  leaves  its  carbon,  in  which  reduced  water 
leaves  its  hydrogen,  in  which  reduced  oxide  of  ammonium  and  nitric 
acid  leave  their  ammonium  or  their  nitrogen"  (20). 

To  appreciate  the  important  and  delicate  role  played  by  hydrogen 
in  animal  life,  one  need  only  recall  that  the  pH  of  the  blood  plasma  never 


188  DISCOVERY   OF  THE  ELEMENTS 

varies  much  from  7.4  (hydrogen  ion  concentration  3.98  X  10~8)>  the 
extreme  pH  limits  compatible  with  life  being  6.9  on  the  acid  side  and 
7.8  on  the  alkaline  side  (21). 

NITROGEN  COMPOUNDS 

Sal  Ammoniac.  In  the  tenth  century  A  D.,  Abu  Musa  Jabir  ibn 
Hayyan  prepared  by  distillation  of  blood  or  hair  a  volatile  product 
which  he  called  "sal  ammoniac  from  blood"  or  "sal  ammoniac  from  hair." 
This  was  probably  "salt  of  hartshorn,"  or  ammonium  carbonate  (23). 

Sal  ammoniac  was  probably  first  introduced  from  Persia  (56).  In 
the  "Invention  of  Verity,  or  Perfection/'  which  has  been  attributed  to 
Pseudo-Geber,  the  preparation  of  sal  ammoniac  from  human  urine, 
perspiration,  common  salt,  and  "soot  of  woods"  is  described  (24,  25). 

Alvaro  Alonso  Barba,  in  his  "Arte  de  los  Metales,"  the  first  edition 
of  which  was  published  in  Madrid  in  1640,  discussed  the  occurrence, 
properties,  and  uses  of  sal  ammoniac  as  follows:  "Among  all  the  Salts 
that  Nature  alone  produceth,  the  scarcest,  but  of  greatest  veitue,  is  the 
Salt- Ammoniac,  they  call  it  vulgarly  Armoniac,  and  from  the  name  con 
clude  that  it  comes  from  Armenia,  but  that  is  not  the  tine  name  of  it, 
but  Ammoniac,  which  in  Greek  signifies  Salt  of  the  sand:  and  under 
neath  the  sand  (of  the  Seashore,  I  suppose),  it  is  found  congealed 
in  little  pieces  by  its  internal  heat  and  the  continued  burning  of  the 
Sun,  baked  so  much  that  it  is  made  the  bitterest  to  taste  of  all  kind 
of  Salt.  Goldsmiths  use  it  more  than  the  Physicians.  It  is  one  of  those 
they  call  the  four  spirits,  because  the  fire  will  convert  them  into  smoak, 
and  so  they  fly  away:  the  other  three  are,  1.  Quicksilver,  2.  Sulphur, 
3.  Saltpeter,  It  hath  a  particular  property  to  cleanse  and  colour  Gold, 
and  is  put  into  the  composition  of  that  Aqua-fortis  that  dissolves  it 
[aqua  regia]"  (26). 

Robert  Boyle  stated  in  1661,  in  his  "Sceptical  Chymist,"  that  sal 
ammoniac  is  composed  of  muriatic  (hydrochloric)  acid  and  the  volatile 
alkali  (ammonia)  and  told  how  to  separate  the  "urinous  and  common 
salts"  (27).  In  1716  Geoffroy  the  Younger  demonstrated  the  composi 
tion  of  sal  ammoniac  and  prepared  it  by  sublimation  (28,  29).  In  the 
same  year,  the  Jesuit  missionary  Father  Sicard  described  its  preparation 
at  Damire  or  Damayer,  one  mile  from  the  City  of  El  Mansura  in  the  Nile 
Delta.  In  twenty-five  large  laboratories  and  several  smaller  ones,  it  was 
sublimed  in  glass  vessels  from  the  soot  of  the  burned  dung  of  camels 
and  cows,  to  which,  he  said,  had  been  added  salt  and  urine,  Lemere, 
the  French  consul  at  Cairo,  described  the  process  in  1719  for  the  Academy 
of  Sciences  in  Paris,  but  made  no  mention  of  salt  or  urine  (29,  30,  31). 


OLD  COMPOUNDS   OF  HYDROGEN   AND   NITROGEN  189 

When  it  was  learned  that  the  Egyptians  did  not  add  salt,  scientists 
were  at  a  loss  to  find  the  source  of  the  muriate  (chlorine)  in  the  sal 
ammoniac  The  first  satisfactory  explanation  was  given  by  Fredrik 
Hasselqvist  (a  student  of  Linne  who  made  a  scientific  journey  through 
Egypt  and  Palestine  in  1749-52)  in  his  first-hand  description  of  the 
manufacturing  process.  According  to  Hasselqvist,  Egyptian  laborers 
spent  the  spring  months  of  each  year  collecting  and  drying  the  dung  of 
horses,  donkeys,  camels,  cattle,  buffaloes,  sheep,  and  goats.  In  Egypt 
most  of  the  wells  are  brackish  and  much  of  the  vegetation  is  rich  in 
salt.  When  domestic  animals  assimilate  these  plants,  they  excrete  some 
of  the  sodium  chloride.  Egyptian  manufacturers  were  therefore  able  to 
prepare  sal  ammoniac  without  adding  salt. 

Since  the  annual  floods  of  the  Nile  abundantly  enriched  the  soil,  large 
quantities  of  animal  manures  could  be  diverted  to  this  manufacturing 
process  without  impoverishing  Egyptian  agriculture.  As  the  dung  was 
burned,  the  soot  from  it  was  collected  and  heated  in  glass  flasks  in  a 
brick  furnace.  'They  make  the  fire  gentle  at  first,"  said  Hasselqvist,  ".  .  . 
they  increase  the  heat  gradually  till  they  bring  it  to  the  highest  degree, 
which  the  workmen  call  hell-fire,  and  continue  it  so  for  three  days  and 
three  nights  together.  When  the  heat  is  come  to  its  due  degree,  the 
smoke  shews  itself  with  a  sourish  smell  that  is  not  unpleasant;  and  in 
a  little  time  the  salt  sticks  to  the  glasses  and  covers  the  whole  aper 
ture  .  .  ."  (32).  When  the  flasks  were  broken,  a  rounded  cake  of 
sublimed  sal  ammoniac  was  removed  from  each  of  them.  Hasselqvist 
inspected  plants  such  as  this  at  Rosetta,  Gizeh,  and  other  places  in  the 
Delta,  each  of  which  had  its  glassworks  for  manufacturing  and  remaking 
them  from  the  broken  glass  (32,  33). 

E.-F.  Geoffrey  stated  that  sal  ammoniac,  because  of  its  volatility  and 
the  manner  in  which  it  used  to  be  prepared,  was  often  called  the  heavenly 
eagle,  the  flying  little  bird,  the  solar  salt,  or  the  mercurial  soot  (43}. 
Herman  Boerhaave  believed  that,  since  Vesuvius  and  other  volcanoes 
eject  sal  ammoniac,  "it  is  therefore  necessary  to  class  this  salt  with  the 
fossils,  although  it  is  believed  that  that  which  is  now  being  brought  to 
us  is  an  animal  production"  (75).  By  the  word  "fossil"  Boerhaave  and 
his  contemporaries  meant  a  mineral,  or  substance  dug  from  the  earth. 

In  1759  Robert  Dossie  corrected  the  false  belief  that  sal  ammoniac 
was  found  in  the  earth  in  Oriental  countries  only  where  the  caravans 
had  rested.  "But  I  know  it  to  be  an  undoubted  fact/'  said  he,  "that  sal 
Ammoniacus  is  sublimed  in  a  considerable  quantity  out  of  the  chinks  or 
cracks  of  the  earth,  in  the  Sulfiterra  (solfatara),  near  Naples  .  .  .  and 
it  is  certain,  as  the  salt  so  sublimed  must  be  raised  from  vast  caverns 
which  lie  deep  in  the  earth,  its  origin  cannot  be  ascribed  to  the  urine 


190  DISCOVERY  OF  THE  ELEMENTS 

of  camels,  in  caravans;  nor  indeed  to  any  other  circumstance  in  which 
the  parts  of  animals  or  vegetables  have  any  concern"  (35). 

Ammonia.  Raimundo  Lulio  (Raymond  Lully)  mentioned  caustic 
ammonia  in  the  thirteenth  century  (36).  Johann  Kunckel  (or  Kunkel) 
von  Lowenstern  (1630-1702)  described  it  in  his  posthumously  pub 
lished  "Vollstandiges  Laboratonum  Chymicum"  (37).  He  prepared  it 
by  adding  lime  to  sal  ammoniac  (38). 

Saltpeter  or  Niter.  "Salt-peter/'  said  P.-J.  Macquer,  ".  .  .  signifies 
the  Salt  of  Stone;  and  in  fact  Nitre  is  extracted  from  the  stones  and 
plaister  in  which  it  forms  .  .  ."  (8).  In  the  chemical  works  of  the 
unknown  monk  "Basil  Valentine/'  which  were  edited  by  Johann  Tholde, 
saltpeter  is  described  as  "a  wonder-salt"  with  an  infernal  spirit  con 
cealed  in  an  ice-like  form. 

"Mein  Form  1st  schlecht  ein  lauter  Eyss/ 
Darin  findst  du  ein  hollschen  Geist"  (39) 

In  1624  a  proclamation  was  issued  in  Cambridge,  England,  for  "the 
preservation  of  Grounds  for  making  of  Salt-Peeter,"  making  it  illegal 
to  pave  dovecots  or  cellars  (except  the  part  used  for  wine  or  beer)  with 
stone,  brick,  or  floor-boards  or  to  lay  the  same  with  "lime,  sand,  gravel, 
or  anything  that  would  stop  the  growth  of  the  Mine  of  Saltpeter"  (40). 

J  R.  Glauber  was  probably  the  first  to  form  artificial  niter  beds. 
By  throwing  putrefiable  matter  of  both  vegetable  and  animal  origin  into 
pits  and  adding  wood  ashes,  he  obtained  in  due  time  a  "saltpeter  earth" 
from  which  he  extracted  a  solution  which,  on  evaporation,  yielded  crystals 
of  this  salt.  Glauber  believed  that  the  function  of  the  putrid  material 
was  merely  "to  draw  the  niter  from  the  air"  (41). 

In  1717  Louis  L6mery  stated  that  saltpeter  was  usually  obtained 
from  die  earth  and  refuse  piles  near  old  lime-plastered  walls  and  in 
stables  and  churchyards,  To  explain  its  origin,  John  Mayow  postulated 
the  existence  of  a  hypothetical  "saltpeter"  in  the  atmosphere.  When 
Mariotte  exposed  to  the  air  of  an  upper  room  some  "saltpeter  earth" 
(earth  from  which  all  the  saltpeter  had  previously  been  leached  out), 
however,  he  was  unable  to  prepare  even  a  gram  of  saltpeter.  When  he 
placed  the  same  earth  in  the  cellar,  it  soon  became  covered  with  salt 
peter,  Lemery  placed  three  earthen  vessels  containing  respectively 
lime,  potassium  carbonate,  and  leached  "saltpeter  earth"  on  pedestals, 
and  exposed  them  to  the  moist  air  of  a  dark  cellar  whose  walls  and 
floor  were  covered  with  saltpeter.  Even  after  two  years,  however,  he 
found  not  a  trace  of  saltpeter  in  any  of  the  three  vessels.  By  frequently 
moistening  the  contents  with  animal  substances,  however,  he  soon  pre 
pared  a  considerable  quantity  of  it  (42). 


OLD   COMPOUNDS    OF   HYDROGEN   AND    NITROGEN  191 


s^yutili'&UK}!1^ 

^t'j&*jH"'Pt'^i|'V]^  Soem.AtyMJA-i  Sm  ••<;*  .lu:?jf.»  :V'*'V^ 


Courtesy  Tenney  L.  Davis 

Etienne-Frangois  Geoffroy,  1672-1731.  French  physician  and  chemist 
known  as  "Geoffrey  the  Elder."  Professor  of  chemistry  at  the  Jardin  du  Roi 
and  physician  to  the  King  of  France.  He  is  most  famous  for  his  table  of 

chemical  affinities. 


192  DISCOVERY  OF  THE  ELEMENTS 

To  distinguish  saltpeter  from  sodium  carbonate  (the  "niter,"  or 
natram,  of  the  ancients)  E.-F.  Geoffrey  called  it  "the  niter  of  the 
moderns.  .  .  .  Since  no  Salt-petre  is  obtainable,"  said  he,  "except  from 
Earths  impregnated  with  the  urinous  Salts  of  Animals  or  Vegetables,  it 
is  doubted  by  some  whether  this  Salt  be  of  a  Mineral  or  Animal  Original. 
This  we  leave  to  be  determined  by  others,  but  we  chuse  to  follow  the 
Example  of  the  Generality  of  Chemists,  in  ranking  it  among  Minerals, 
because  it  is  extracted  immediately  from  the  Earth,  and  cannot  be  ob 
tained  from  the  Urine  and  Faeces  of  Animals  without  Earth"  (43). 

His  contemporary  Dr.  Herman  Boerhaave  said  that  "Modern  niter, 
or  saltpeter,  forms  octagonal  crystals:  it  is  a  semi-fossil  extracted  from 
a  bitter  nitrous  earth;  it  melts  in  a  moderate  fire;  it  gives  off  very  little 
water;  it  is  rather  fixed;  when  it  is  melted,  it  bursts  into  flame  with  all 
inflammable  matter;  it  dissolves  in  6l/2  (parts)  of  water"  (34). 

After  mentioning  the  use  of  saltpeter  in  gunpowder,  Boerhaave 
wrote:  "May  it  please  Heaven  that  men,  no  longer  ingenious  in  finding 
means  of  destroying  one  another,  may  cease  from  cruelly  waging  war 
on  each  other  and  no  longer  employ  to  their  own  destruction  the  beautiful 
inventions  of  a  science  in  itself  so  salutary.  Therefore  I  feel  compelled  to 
remain  silent  regarding  several  other  discoveries  more  dangerous  and 
more  detestable"  (34). 

A  small  saltpeter  refinery  was  in  operation  in  Dijon,  France,  as 
early  as  1725,  Itinerant  saltpeter-makers,  authorized  by  the  government 
to  collect  earth  from  the  stables  and  cellars  of  the  inhabitants,  also  de 
manded  from  them  free  lodging  and  wood  for  heating  their  evaporating 
kettles  (44).  In  the  latter  part  of  the  eighteenth  century  Lavoisier 
greatly  improved  the  French  saltpeter  industry  (45).  In  1778  Guyton  de 
Morveau,  Jean-Baptiste  Courtois,  and  others  founded  a  plant  at  Dijon 
for  the  artificial  production  of  saltpeter,  which  was  unable  to  compete 
with  the  cheap  product  from  India.  During  the  French  Revolution, 
however,  J,-B.  Courtois  found  the  business  lucrative,  His  son,  Bernard, 
while  scarcely  more  than  a  child,  began  to  help  in  the  plant  and  to  show 
an  intelligent  interest  in  the  process. 

To  convert  the  alkaline  earth  nitrates  into  saltpeter,  Bernard  and 
his  father  added  wood  ashes.  Since  much  of  the  potash  from  the  ashes 
was  wasted  by  reacting  with  salts  other  than  nitrates,  they  conceived  the 
idea  of  using,  instead  of  wood  ashes,  the  cheaper  ash  of  sea-weeds, 
especially  Fucus  and  Laminaria  from  the  coasts  of  Normandy  and 
Brittany.  The  resulting  sodium  nitrate  was  then  economically  con 
verted  to  potassium  nitrate  by  treatment  with  wood  ashes,  The  ash 
of  these  algae  contains  sodium,  potassium,  magnesium,  and  calcium  as 


OLD   COMPOUNDS   OF  HYDROGEN   AND    NITROGEN  193 

chlorides,  bromides,  iodides,  carbonates,  and  sulfates,  but  was  then 
valued  only  for  its  alkali  content  (44). 

Volume  1  of  the  American  Journal  of  Science  contains  a  first-hand 
description,  by  Dr.  Samuel  Brown,  of  the  niter  caves  of  Kentucky,  which 
have  been  known  since  the  beginning  of  the  nineteenth  century  (46). 
R,  N.  Maxson  described  these  caves  in  the  Journal  of  Chemical  Education 
for  November,  1932  (47). 

Chilean  Nitrate  Chile  saltpeter,  or  sodium  nitrate,  was  probably 
known  to  the  South  American  Indians  before  the  coming  of  the  Spaniards 
(48).  The  first  Englishman  to  visit  the  nitrate  coast  (then  part  of 
southern  Peru)  was  Sir  Francis  Drake  in  1578.  Eight  years  later, 
Lopez  Vaz,  a  Portuguese,  told  Captain  Withrington  that  "Peru  ,  .  . 
hath  many  mines  of  gold  and  more  of  silver,  as  also  great  store  of  copper 
and  tinne-mines  with  abundance  of  salt  peter  and  brimstone  to  make 
gun-pouder"  (48,  49,  50).  The  Indians  near  Lima  used  to  purify  the 
nitrate  and  covert  it  into  gunpowder  for  use  in  the  mercury  mines  at 
Huancavelica  and  in  their  fireworks.  In  the  nineteenth  century,  Chile 
saltpeter  was  shipped  to  Europe  for  manufacturing  rockets  for  saint-day 
displays  in  Catholic  countries  ( 48 ) . 

LITERATURE  CITED 

( 1 )  HILL,   JOHN,   "Theophrastus's   History   of   Stones/'   2nd   ed ,   printed   for   the 

translator,  London,  1774,  pp.  225,  227-35 

( 2 )  GLAUBER,   J.   R ,  "A  Description  of  New  Philosophical   Furnaces/1  Richard 

Coats,  London,  1651-2.     Preface  by  J.  F.,  the  English  translator,  also  pp 
10-13,  31,  76-8,  96-7. 

(3)  SODERBAUM,  H    G.,  "Jac   Berzelius.  Levnadsteckning/'  Vol.  2,  P.  A.  Norstedt 

and  Sons,  Stockholm,  1929-31,  pp.  54-7. 

(4)  Ibid.,  Vol.  1,  p.  187. 

(5)  BUGGE,  GTTNTHER,,  "Das  Buch  der  grossen  Chemiker/*  Vol    1,  Verlag  Chemie, 

Berlin,  1929,  pp.  60-9      Chapter  on  Pseudo-Geber  by  Julius  Ruska. 

(6)  KOPP,   HERMANN,  "Geschichte  der  Chemie/7  Vol,   3,   F.  Vieweg   and  Son, 

Braunschweig,  1847,  pp    225-32. 

(7)  DOSSIE,  ROBERT,  "Institutes  of  Experimental  Chemistry/*  Vol.  1,  J.  Nourse, 

London,  1759,  p.  334. 

(8)  MACQUER,  P  -J.,  "Elements  of  the  Theory  and  Practice  of  Chymistry/'  2nd  ed., 

Vol.  1,  A   Millar  and  J.  Nourse,  London,  1764,  pp.  28-9,  32,  241. 

(9)  KOPP,  HERMANN,  ref.  (6),  Vol.  3,  pp   303-9. 

(10)  MACQUER,  P-J.3  "Chyrmsches  Worterbuch,"  German  translation  from  the  2nd 

French  ed ,  Vol   6,  Weidmanmsche  Buchhandlung,  Leipzig,  1790,  pp.  763- 
92 

(11)  "Encyclopedic  methodique,"  Vol.  1,  Panckoucke,  Paris,  1786,  pp.  353-97. 

(12)  STEPHEN,  L.  and  S.  LEE,  "Dictionary  of  National  Biography/'  Vol.  17,  Oxford 

University  Press,  London,  1921-2,  pp.  93-5.     Article  on  John  Roebuck  by 
Francis  Espinasse. 

(13)  Ibid,  Vol  20,  pp  783-5.    Article  on  Joshua  Ward  by  E.  I.  Carlyle. 

(14)  MACTEAR,  JAMES,  "On  the  growth  of  the  alkali  and  bleaching-powder  manu 

facture  of  the  Glasgow  district,"  Chem.  News,  35,  14-17  (Jan.  12,  1877). 


194  DISCOVERY  OF  THE  ELEMENTS 

(15)  SODERBAUM,  H.  G.,  "Jac.  Berzelms.     Reseantecknmgar,"  P.  A.  Norstedt  and 

Sons,  Stockholm,  1903,  pp.  171-3. 

(16)  KOPP,  HERMANN,  Ref.  (6),  Vol.  3,  pp   348-53;  Vol.  4,  pp.  82-9. 

(17)  "Fr.   Basilii  chymische  Scliriften,"  revised  ed.,   part  1,   Gottfried  Liebezeit, 

Hamburg,  1694,  pp.  281-2. 
(IS)     GLAUBER,   J.   R,   "Opera  chymica,"  T.   M.   Gotzen,   Frankfort-on-the   Mam, 

1658.,  p.  52     Second  part  of  the  Pharmacopaeae  Spagyncae. 
(J9)     "On  muriatic  acid  in  the  stomach/'  Quarterly  J  ScL,  17,  181  (1824). 

(20)  DUMAS,  J.-B.  and  BOUSSINGAULT,  J.-B  ,  "Essai  de  statique  chimique  des  etres 

organises,"  3rd  ed.,  Fortin,  Masson  et  Cie.,  Pans,  1844,  pp   5,  27-8,  140 

(21)  SHOHL,  A.  T,  "Mineral  Metabolism/7  Reinhold  Publishing  Corporation,  New 

York,  1939,  pp.  28  and  282. 

(22)  "Taschen-Buch  fur  Scheidekunstler  und  Apotheker/'  Hoffmann  Buchhandlung, 

Weimar,  1782,  pp.  109-21 

(23)  BUGGE,  G,  "Das  Buch  der  grossen  Chemiker,"  Vol   1,  Verlag  Cherme,  Berlin, 

1929,  p.  28.     Article  on  Dschabar  (Jabir  or  Geber)  by  J    Ruska. 

(24)  HOLMYARD,  E.  J  ,  "The  Works  of  Geber,  Englished  by  Richard  Russell,  1678," 

J.  M.  Dent  and  Sons,  London  and  Toronto,  1928,  pp.  205-6 

(25)  DARMSTAEDTER,  EPNST^  "Die  Alchemie  des  Geber/'  Julius  Springer,  Berlin, 

1922,  pp,  105-6. 

(26)  BABBA,  A.  A.,  "The  Art  of  Metals,"  S.  Mearne,  London,  1674,  pp.  29-30,  90-1. 

(27)  BOYLE,   ROBERT,   "The   Sceptical  Chymist,"  J.    M    Dent  and   Sons,   London 

(undated  reprint),  p.  47. 

(28)  GEOFFROY  THE  YOUNGER,  "Beobachtungen  uber  die  Natur  und  Mischung  des 

Salmiaks,"  Crell's  Neues  chem.  Archiv,  2,  60-79,  157-67  (1784);  M<§m.  de 
1'Acad.  des  Sciences  (Pans),  1716,  1720,  1723. 

(29)  "Anzeige  an  die  Akademie  uber  den  Salmiak,  usw.  von  Lemere,  Consul  in 

Cairo,  den  24sten  Junii,  1719/'  C fell's  Neues  chem.  Archiv,  2,  61-5 
(1784). 

(50)  BECKMAN,  JOHANN,  "A  histoiy  of  Inventions,  Discoveries,  and  Origins,"  4th 

ed.,  Vol.  2,  Henry  G.  Bohn,  London,  1846,  pp.  402-7 

(51)  "Recueil  des  me"moires  de  chymie  .  .  .  contenus  dans  les  Actes  de  1'Acad. 

d'Upsal  et  dans  les  m&noires  de  TAcad.  Roy.  des  Sciences  de  Stockolm 
[sic]  .  .  .  ,"  P-F.  Didot  le  jeune,  Paris,  1764,  pp  227-36  (M  C.  Leyel  on 
sal  ammoniac),  LEVEL,  Vet  Acad.  Handl.,  13  (1751). 

(82)  HASSELQVIST,  F.,  "Iter  Palaestinum  eller  resa  till  Hehga  Landet,"  Lars  Salvius, 
Stockholm,  1757,  pp.  540-3,  "Voyages  and  Travels  in  the  Levant/'  L.  Davis 
and  C.  Reymers,  London,  1766,  pp.  304-7. 

(33)  "Recueil  des  Memoires/'  ref,   (SI),  pp.  237-43,     F.  Hasselqvist  on  Sal  am 

moniac. 

(34)  BOERHAAVE,  H.,  "El^menS  de  chymie/*  Vol.  1,  Chardon  fils,  Pans,  1754,  pp. 

88,  90S  215 

(35)  DOSSIE,  ROBERT,  ref.  (7),  Vol.  1,  pp  319,  354. 

(36)  DARMSTAEDTER,  LXTOWIG,  "Handbuch  zur  Geschichte  der  Naturwissenschaften 

und  der  Technik/'  2nd  ed.,  J  Springer,  Berlin,  1908,  p   55. 

(37)  Ibid.,  p.  158. 

(33)     KUNKEL  VON  LOWENSTERN,  JOHANN?  "Vollstandiges  Laboratorium  Chymicum," 

4th  ed.,  Rudigersche  Buchhandlung,  Berlin,  1767,  p,  459, 
(35)     "Fr.  Basilii  Valentim  Chymische  Schriften/'  ref.  (17),  pp    157-8. 

(40)  GUNTHER,  R.  T,,  "Early  Science  in  Cambridge,"  University  Press,  Oxford, 

1937,  p.  219. 

(41 )  MASSEY,  JAMES,  "A  treatise  on  saltpetie/'  Memoirs  Lit.  and  Philos.  Soc.  (Man 

chester),  L,  184-223  (1789). 

(42)  LEMERY,  L.,  "Ueber  den  Salpeter,"  Crell's  Neues  chem,  Archiv,  1,  159-75 

(1784),  Hist,  de  1'Acad.  Roy.  des  Sciences,  1717. 


OLD   COMPOUNDS   OF  HYDROGEN   AND    NITROGEN  195 

(43)  GEOFFROY,  E.-F.,  "Treatise  of  the  Fossil,  Vegetable,  and  Animal  Substances 
That  Are  Made  Use  of  in  Physick,"  W.  Innys,  R.  Manby,  et  al.,  London, 
1736,  pp  96-7,  123. 

(44}  TORAUDE,  L -G,,  "Bernard  Courtois  et  la  decouverte  de  Tiode/*  Vigot  Freres, 
Pans,  1921,  164  pp. 

(45)  GRIMAUX,  E.,  "Lavoisier,  1743-1794,"  Felix  Alcan,  Pans,  1888,  pp.  82^-96. 

(46)  BROWN,  SAMUEL,  "On  a  curious  substance  which  accompanies  the  native  nitre 

of  Kentucky  and  of  Africa,"  Am  J.  ScL,  1,  146-8  (1819). 

(47)  MAXSON,  R.  N,  "The  niter  caves  of  Kentucky,"  J.  Chem.  Educ ,  9,  1847-64 

(Nov.,  1932) 

(48)  DONALD,  ME.,  "History  of  the  Chile  nitrate  industry,"  Annals  of  Sci.,  1,  29- 

47,  193-216  (1936). 

(49)  "The  History  of  Lopez  Vaz,  a  Portugall,  Taken  by  Captaine  Withrington  at 

the  River  of  Plate,  Anno  1586  Purchas  his  pilgrimes,"  Vol  17,  James 
MacLehose  and  Sons,  Glasgow,  1906,  p.  283 

(50)  HAKLUYT,    RICHARD,    "The   Principal    Navigations,   Voyages,    Traffiques,    and 

Discoveries  of  the  English  Nation,"  Vol.  8,  J.  M.  Dent  and  Co.,  London 
(undated  reprint),  p.  199.  **A  discourse  of  the  West  Indies  and  South  Sea, 
written  by  Lopez  Vaz,  a  Portugal " 

(51)  LE  FEVRE,  NICOLAS,  "Corns  de  chymie,"  5th  ed.,  Vol    1,  J -N.  Leloup,  Paris, 

1751,  p.  1. 

(52)  ARMSTRONG,  EVA  V    and  C.  K.  DEISCHER,  "Johann  Rudolf  Glauber  (1604- 

70),"  J.  Chem.  Educ.,  19,  3-8  (Jan.,  1942). 

(53)  JORISSEN,  W.  P.,  "lets  over  Glauber's  Amsterdamschen  Tijd,"  Chem.  WeekbL, 

15,  268-71  (1918). 

(54)  GLASSTONE,  SAMUEL,  "William  Prout  (1785-1850),"  J  Chem.  Educ.,  24,  478- 

81  (Oct.,  1947). 

(55)  PROUT,  WILLIAM,   "'Chemistry,   Meteorology,  and  the  Function  of  Digestion 

Considered  with  Reference  to  Natural  Theology,"  William  Pickering,  Lon 
don,  1834,  499-500 

(56)  RUSKA,  JULIUS,  Z.  angcw.  Chcmie,  41,  1321  (1928) 


Courtesy  D,  I.  Duveen 
and  H,  S.  Klickstein 


Antoine-Laurent  Lavoisier,  Bronze  medal  by  Abel  Lafleur  honor 
ing  the  memory  of  Lavoisier,  founder  of  modern  chemistry,  on  the 
bicentenary  of  his  birth.  It  reads:  "He  is  perhaps  the  most  com 
plete,  the  greatest  man  that  France  has  produced  in  the  Sciences" 

(J.  B,  Dumas). 


"The  generality  of  men  are  so  accustomed  to  judge 
of  things  by  their  senses  that,  because  the  air  is  in 
visible,  they  ascribe  but  little  to  it,  and  think  it  but 
one  remove  from  nothing."  (1) 


7 


Three  important  gases 


Chemists  of  the  eighteenth  century  were  intensely  interested  in 
"air"  which  they  prepared  by  fermentation,  by  heating  various 
chemical  compounds,  and  by  allowing  substances  of  vegetable 
and  animal  origin  to  putrefy.  Gradually  the  idea  dawned  that, 
as  Priestley  expressed  it,  there  are  "different  kinds  of  air"  and 
that  Cavendish's  "inflammable  air  from  metals3"  is  quite  different 
from  Daniel  Rutherford's  "noxious  air"  and  from  Scheele's  "fire 
air."  The  preparation  and  recognition  of  the  three  gases,  hydro 
gen,  nitrogen,  and  oxygen,  required  true  genius.  For  further 
information  about  Rutherford  see  pp.  235-51. 


L 


n  the  latter  part  of  the  seventeenth  century,  Johann  Joachim 
Becher  and  Georg  Ernst  Stahl  advanced  a  peculiar  theory  of  combustion 
that  held  sway  over  the  minds  of  chemists  for  nearly  a  hundred  years. 
They  maintained  that  everything  that  can  be  burned  contains  a  substance, 
phlogiston,  which  escapes  in  the  form  of  flame  during  the  combustion, 
and  until  Lavoisier  overthrew  this  theory  in  1777,  practically  all  chemists 
believed  that  a  metal  consists  of  its  calx,  or  oxide,  and  phlogiston.  It 
was  in  this  period  of  chemical  history  that  the  gases  hydrogen,  nitrogen, 
and  oxygen  were  discovered. 

HYDROGEN 

Hydrogen  was  observed  and  collected  long  before  it  was  recognized 
as  an  individual  gas.  The  statement  of  Paracelsus  (1493-1541)  that 
"Luft  erhebt  sich  und  bricht  herfiir  gleichwie  ein  Wind"*  has  often  been 
cited  erroneously  as  an  allusion  to  this  gas  (2,  37),  Van  Helmont,  Boyle, 
Mayow,  and  Stephen  Hales  all  had  some  slight  acquaintance  with  hydro 
gen.  In  his  "New  experiments  touching  the  relation  betwixt  flame  and 
air,"  which  were  ready  for  publication  in  1671,  Robert  Boyle  dissolved 
iron  in  dilute  hydrochloric  or  sulfuric  acid  and  prepared  hydrogen  in  the 
form  of  "inflammable  solution  of  Mars  [iron]"  (44). 

*  "Air  rises  and  breaks  forth  like  a  wind." 

197 


198 


DISCOVERY  OF  THE  ELEMENTS 


"Having  provided  a  saline  spirit  [hydrochloric  acid],"  said  Boyle, 
".  .  .  we  put  into  a  vial,  capable  of  containing  three  or  four  ounces  of 
water,  a  very  convenient  quantity  of  filings  of  steel,  which  were  not  such 
as  are  commonly  sold  in  shops  to  chemists  and  apothecaries  (those  being 
usually  not  free  enough  from  rust)  but  such  as  I  had  a  while  before 
caused  to  be  purposely  filed  off  from  a  piece  of  good  steel,  This  metalline 
powder  being  moistened  in  the  vial  with  a  little  of  the  menstruum,  was 
afterwards  drenched  with  more;  whereupon  the  mixture  grew  very  hot, 
and  belched  up  copious  and  stinking  fumes,  which  whether  they  con- 


Georg  Ernst  Stahl,  1660-1734.  Ger 
man  chemist,  physician,  and  professor. 
Co-founder  of  the  phlogiston  theory  of 
combustion.  Author  of  "Fundamenta 
Chymiae  Dogmaticae  et  Expenmen- 
talis,"  He  distinguished  between  pot 
ash  and  soda  and  recognized  that  alum 
contains  a  pecukar  earth  different  from 
all  others. 


From  Bugged  "Das  "Buck  der  grossen  Chemiker" 


sisted  altogether  of  the  volatile  suphur  of  the  Mars,  or  of  metalline  steams 
participating  of  a  sulphureous  nature,  and  joined  with  the  saline  exhala 
tions  of  the  menstruum,  is  not  necessary  to  be  here  discussed.  But 
whencesoever  this  stinking  smoke  proceeded.,  so  inflammable  it  was, 
that  on  the  approach  of  a  lighted  candle  to  it,  it  would  readily  enough 
take  fire  and  burn  with  a  blueish  and  somewhat  greenish  flame  at  the 
mouth  of  the  vial  for  a  good  while  together;  and  that,  though  with  little 
light,  yet  with  more  strength  than  one  would  easily  suspect"  (44). 

Nicolas  L&nery  described  it  in  1700  in  the  M6moires  of  the  Paris 
Academy  (2).  In  the  1686  English  edition  of  his  "Course  of  Chyrnistry," 
which  was  based  on  the  fifth  French  edition,  there  is  no  mention  of  the 
evolution  of  any  flammable  or  explosive  gas  when  "vitriol  of  Mars"  is 
prepared  by  dissolving  iron  in  dilute  sulfuric  acid,  At  that  time,  L6mery 


THREE  IMPORTANT  GASES 


199 


wy  ner  jTfn  ,  fs 


.- 

Courtesy  Dr.  Claude  K.  "Deischer,  Edgar  Fahs  Smith  Memorial  Collection 


Johann  Joachim  Becher,  1635-1682.  German  chemist  and  physician.  Founder 
of  the  phlogiston  theory.  His  experiments  on  minerals  are  described  in  his 
"Physica  Subterranea."  Stahl  summarized  his  views  on  combustion  in  a  book 

entitled  "Specimen  Becherianum." 


200 


DISCOVERY  OF  THE  ELEMENTS 


merely  observed  that  "the  hquor  heats  and  boils  considerably"  (45), 
In  the  eleventh  French  edition,  however,  which  was  published  in  1716, 
a  year  after  Le'mery's  death,  the  same  preparation  is  described  as  yielding 
"white  vapors  which  will  rise  to  the  top  of  the  neck  of  the  matrass,  if  one 
presents  a  lighted  candle  to  the  mouth  of  this  vessel,  the  vapor  will 
immediately  take  fire  and  at  the  same  time  produce  a  violent,  shrill 
fulmination"  (45).  In  this  reaction  Lemery  believed  he  had  found  the 
cause  of  thunder  and  lightning, 

Hermann  Kopp  stated  in  his  "Geschichte  der  Chemie"  that  at  the 
beginning  of  the  seventeenth  century  Turquet  de  Mayerne  (1573-1655) 
noticed  the  flammability  of  the  gas  evolved  from  a  mixture  of  iron  and 
sulfuric  acid  and  was  the  first  to  make  this  observation  (2).  Brief  ac 
counts  of  the  life  and  work  of  Turquet  de  Mayerne  may  be  found  also 
in  Dr.  Charles  H.  LaWall's  "The  Curious  Lore  of  Drugs  and  Medicines" 
(64)  and  Dr.  Victor  Robinson's  "The  Story  of  Medicine"  (65). 

The  name  most  closely  associated  with  the  early  history  of  hydrogen 
is  that  of  Mr.  Henry  Cavendish,  Although  he  was  a  descendant  of  the 


Henry  Cavendish,  1731-1810.  English 
chemist  and  physicist.  This  is  the  Alex 
ander  portrait.  The  likeness  of  Caven 
dish  in  W.  Walker's  engraving  of  British 
scientists  was  taken  from  the  drawing  hy 
Tomlinson  (46).  Cavendish  was  the 
first  to  distinguish  hydrogen  from  other 
gases  and  was  an  independent  discoverer 
of  nitrogen. 


Dukes  of  Devonshire  and  the  Dukes  of  Kent,  he  was  born  at  Nice;  for 
his  mother,  Lady  Anne  Cavendish,  had  gone  to  France  for  the  benefit 
of  the  mild  climate,  The  date  of  his  birth  is  given  as  October  10,  1731. 
The  unfortunate  death  of  Lady  Cavendish  two  years  later,  and  the  con 
sequent  lack  of  maternal  affection  in  the  young  child's  life  may  account 


THREE   IMPORTANT  GASES  201 

in  some  degree  for  the  abnormal  shyness  and  ungregariousness  of  the 
man.  At  the  age  of  eleven  years  Henry  Cavendish  entered  Dr.  New- 
come's  school  at  Hackney,  and  from  1749  to  1753  he  attended  Cambridge 
University.  Although  he  lacked  only  a  few  days  of  the  necessary  residence 
requirements,  he  left  Cambridge  without  receiving  a  degree  (3). 


From  Edivai  d  Smith's  "Life  of  Sir  Joseph  Batiks" 
Lady   Banks  Sir  Joseph  Banks 

(From  a  Wedgwood  cameo,  attributed  to  Flaxman  ) 

Sir  Joseph  Banks,  1743-1820.  English  naturalist  and  collector  of  plants  and 
insects  President  of  the  Royal  Society  from  1778-1820.  His  collections  of 
books  and  natural  history  specimens  were  bequeathed  to  the  British  Museum. 
Lady  Banks  used  to  assist  him  in  giving  frequent  receptions  for  the  scientists 

of  London 


During  his  father's  lifetime  Cavendish  lived  on  a  meager  allowance, 
but,  upon  his  father's  death  in  1783,  he  received  an  enormous  inheri 
tance.  Not  long  after  this  an  aunt  died,  leaving  him  another  large  legacy. 
Thus  he  became,  as  Biot  said,  "the  richest  of  all  the  learned  and  the  most 
learned  of  all  the  rich"  (4).  Since  Cavendish  lived  very  modestly,  the 
interest  on  his  money  accumulated  until,  at  the  time  of  his  death,  he  was 
the  largest  depositor  in  the  Bank  of  England  (5). 

It  may  be  said  without  exaggeration  that,  of  all  great  personages  of 
scientific  history,  Mr.  Henry  Cavendish  was  the  most  singular.  He  was 
shy  and  awkward  among  strangers,  and  to  him  all  men  were  strangers. 
The  only  social  contacts  he  ever  made  were  at  the  meetings  of  the  Royal 


202  DISCOVERY   OF  THE  ELEMENTS 

Society  and  at  the  Sunday  evening  receptions  which  Sir  Joseph  Banks 
was  accustomed  to  give  for  the  scientists  in  London.  Cavendish  spoke 
falteringly  in  shrill  tones  and  was  unable  to  converse  with  more  than  one 
person  at  a  time;  yet,  because  of  his  broad  knowledge  and  clear  reasoning, 
the  members  of  the  Royal  Society  all  lecognized  him  as  a  superior.  Dr. 
Thomas  Thomson  in  his  well-known  "Histoiy  of  Chemistry"  cites  a 
striking  example  of  Cavendish's  extreme  fear  of  publicity.  Dr,  Jan 
Ingenhousz  once  brought  as  his  guest  to  the  home  of  Sir  Joseph  Banks 
a  distinguished  Austrian  scientist,  whom  he  introduced  to  Cavendish  with 
extravagant  praise.  The  foreign  guest,  in  turn,  became  profuse  m  his 
flattery  of  Cavendish,  stating  that  he  had  come  to  London  with  the  ex 
press  purpose  of  meeting  such  a  distinguished  scientist,  whereupon  Caven 
dish,  at  first  embarrassed,  then  utterly  confused,  darted  thiough  the 
crowd  to  his  waiting  carriage  (5). 

A  few  scientists,  however,  knew  how  to  overcome  his  extreme 
diffidence,  and  of  these  perhaps  the  most  successful  was  Dr.  W.  H.  Wollas- 
ton.  "The  way  to  talk  to  Cavendish,"  said  he,  "is  never  to  look  at  him, 
but  to  talk  as  it  were  into  vacancy,  and  then  it  is  not  unlikely  but  you  may 
set  him  going"  ( 6 ) . 

In  spite  of  his  love  of  solitude,  Cavendish  was  not  lacking  in  interest 
in  the  researches  carried  out  by  others.  He  presented  young  Humphry 
Davy  with  some  platinum  for  his  experiments,  and  went  occasionally  to 
the  Royal  Institution  to  see  his  brilliant  experiments  on  the  decomposition 
of  the  alkalies  ( 6 ) .  Sir  Humphry  said  later  in  his  eulogy  of  Cavendish, 

.  .  .  Upon  all  subjects  of  science  he  was  luminous  and  profound;  and  in 
discussion  wonderfully  acute  .  .  .  His  name  will  be  an  object  of  more  venera 
tion  in  future  ages  than  at  the  present  moment  Though  it  was  unknown  m  the 
busy  scenes  of  life,  or  in  the  popular  discussions  of  the  day,  it  will  remain  illus 
trious  in  the  annals  of  science,  which  are  as  imperishable  as  that  nature  to  which 
they  belong;  and  it  will  be  an  immortal  honour  to  his  house,  to  his  age,  and  to 
his  country  (7). 

Cavendish  dressed  like  an  English  gentleman  of  a  bygone  day  He 
wore  a  cocked  hat  and  a  gray-green  coat  with  a  high  collar  and  frilled 
cuffs.  His  costume  and  personality  are  well  depicted  in  the  famous  Alex 
ander  portrait,  sketched  hastily  at  a  dinner  without  Cavendish's  knowl 
edge.  Cavendish  had  three  residences:  one  near  the  British  Museum, 
furnished  mainly  with  books  and  apparatus;  another  in  Dean  Street, 
Soho,  containing  his  main  library,  which  he  generously  placed  at  the 
disposal  of  all  scholars  who  wished  to  use  it;  and  a  thud  dwelling  known 
as  Cavendish  House,  Clapham  Common.  This  suburban  home  at  Clap- 
ham,  his  favorite  residence,  he  converted  almost  entirely  into  workshops 
and  laboratories  (S). 


THREE  IMPORTANT  GASES 


203 


Although  many  historians  of  chemical  progress  mention  Cavendish 
as  the  discoverer  of  hydrogen,  he  himself  made  no  such  claim  and  pref 
aced  his  remarks  on  the  explosibility  of  a  mixture  of  hydrogen  and  air 
with  the  words,  ",  .  .  it  has  been  observed  by  others.  .  .  "  He  was,  how 
ever,  the  first  to  collect  gases  over  mercury  (41 )  and  distinguish  hydrogen 


From  Thorpe's  "Scientific  Papers  of  the  Hon.  Henry  Cavendish" 
Cavendish's  House  at  Claphara 

from  other  gases  by  the  descriptive  term,  "inflammable  air  from  the 
metals."  His  accurate  description  of  its  properties  and  his  methods  of 
obtaining  the  pure  gas  from  different  sources  were  scientific  contributions 
of  the  first  rank.  He  had,  however,  the  mistaken  idea  that  the  hydrogen 
came  from  the  metal  rather  than  from  the  acid  (9) .  He  at  first  identified 
hydrogen  with  phlogiston,  but  later  thought  it  was  a  compound  of 

phlogiston  and  water. 

Cavendish's  death  was  as  lonely  as  his  life.  He  lived  to  the  age  of 
seventy-nine  years,  and  then,  one  day,  feeling  the  approach  of  death,  he 
asked  an  attendant  servant  to  leave  the  room  and  not  return  until  a 


204  DISCOVERY  OF  THE  ELEMENTS 


Photograph  Z?y  Bachrach 

Harold  Clayton  Urey,  1893-  .  Professor  of  chemistry 
at  the  Institute  for  Nuclear  Studies  at  the  University 
of  Chicago  and  at  the  University  of  California.  In 
1931  Dr.  Urey  and  his  collaborators  discovered  deu 
terium,  the  heavy  isotope  of  hydrogen.  He  has  carried 
out  notable  researches  on  the  entropy  of  gases  and  on 
the  properties  and  separation  of  isotopes  and  has 
studied  the  chemical  evidence  of  the  earth's  origin. 


specified  time.  When  the  servitor  returned,  he  found  his  great  master 
dead  (10).  Mr.  Henry  Cavendish  was  given  the  honor  of  a  public 
funeral  and  burial  in  All  Hallows  Church  near  the  tomb  of  his  philan 
thropic  ancestor,  Elizabeth  Hardwicke.  He  lived  a  blameless  life, 
unselfishly  devoted  to  the  advancement  of  science.  His  researches  in 
cluded  electricity,  astronomy,  meteorology,  and  chemistry,  and  he  was 
also  well  versed  in  mathematics,  mining,  metallurgy,  and  geology.  He 
was  a  great  scientist  in  the  fullest  sense  of  the  word. 

In  December,  1931,  H.  C.  Urey,  F.  G.  Brickwedde,  and  G.  M.  Murphy 
of  Columbia  University  detected,  in  the  residue  from  a  large  amount  of 


THREE  IMPORTANT   GASES  205 

liquid  hydrogen  that  had  been  allowed  to  evaporate  down,  two  very 
faint  lines  near  the  B aimer  lines  in  the  spectrum  of  ordinary  atomic 
hydrogen  (81 ).  By  application  of  quantum  mechanics  they  showed  that 
the  measured  separations  of  these  faint  lines  from  the  more  intense  lines 
of  hydrogen  must  be  due  to  a  hydrogen  atom  of  mass  two,  which  they 
named  deuterium, 

In  July,  1932,  Professor  Urey  and  Di\  Edward  W.  Washburn  of 
the  U.  S.  Bureau  of  Standards  found  that  when  water  is  separated 
into  its  constituents  electrolytically,  i.  e ,  when  a  current  of  electricity 
is  passed  through  water  containing  a  little  sulfuric  acid  to  make  it  con 
duct  the  current,  the  water  remaining  in  the  container  becomes  heavier 
and  heavier  (62}.  Dr,  Urey  and  his  collaborators  found  that  this  in 
crease  in  weight  is  caused  by  the  presence  of  deuterium.  Since  deuterium 
is  twice  as  heavy  as  ordinary  hydrogen,  its  discovery  convincingly  dis 
proved  the  idea  that  isotopes  of  a  given  element  ( atomic  species  of  the 
same  atomic  number  but  different  atomic  weights)  necessarily  have 
identical  chemical  properties  and  are  inseparable  by  chemical  means 
Deuterium  and  hydrogen  are  easily  separated, 

The  history  of  tritium,  the  extremely  rare  hydrogen  isotope  of  mass 
three,  has  been  reported  in  the  Journal  of  Chemical  Education  (81). 

NITROGEN 

The  discovery  of  nitrogen  was  announced  in  a  doctor's  dissertation 
by  Daniel  Rutherford,  uncle  of  Sir  Walter  Scott  (11,  40).  He  was  a 
son  of  Dr.  John  Rutherford,  one  of  the  founders  of  the  Medical  School 
at  Edinburgh,  and  was  born  in  that  city  on  November  3,  1749,  Prepara 
tory  to  entering  his  father's  profession,  he  graduated  from  the  Arts 
course  at  the  University  of  Edinburgh,  and  on  September  12,  1772,  lie 
received  the  degree  of  doctor  of  medicine.  His  dissertation  was  the 
result  of  a  research  suggested  and  directed  by  the  famous  Scottish 
chemist,  Dr.  Joseph  Black.  Dr.  Black  had  noticed  that  when  a  carbon 
aceous  substance  was  burned,  a  certain  amount  of  air  remained  even 
after  the  "fixed  air"  (carbon  dioxide)  had  all  been  absorbed  by  caustic 
potash.  He  therefore  gave  to  Rutherford  the  problem  of  studying  the 
properties  of  this  residual  "air**  ( 12,  38 ) , 

Rutherford  found  that  when  a  mouse  was  left  in  a  confined  volume 
of  air  until  it  died,  one-sixteenth  of  the  volume  disappeared;  and  that 
when  the  remaining  air  was  treated  with  alkali,  it,  in  turn,  lost  one- 
eleventh  of  its  volume.  After  thus  removing  the  carbon  dioxide  (''fixed, 
or  mephitic3  air")  and  most  of  the  oxygen,  he  studied  the  properties  of 
the  residual  gas,  He  found  it  very  difficult  "to  completely  saturate  air 
with  phlogiston."  (to  remove  all  the  oxygen),  for  after  a  mouse  had  died 


206  DISCOVERY  OF  THE  ELEMENTS 

in  it,  a  candle  would  burn  feebly,  and  after  the  flame  had  nickered  out, 
the  candle  wick  or  phosphorus  would  continue  to  glow.    His  best  results 


Joseph      Black,      1728-1799. 

Scottish  chemist,  physicist, 
and  physician.  Professor  of 
chemistry  at  Glasgow.  He 
clearly  characterized  carbon 
dioxide  ("fixed  air")  as  the 
gas  which  makes  caustic  alka 
lies  mild,*  and  distinguished 
between  magnesia  and  lime. 
He  discovered  the  latent  heats 
of  fusion  .and  vaporization, 
measured  the  specific  heats  of 
many  substances,  and  invented 
an  ice  calorimeter, 


Courtesy  Lytnan  C    Newell 


were  obtained  by  burning  phosphorus  in  the  confined  air.  Since  the  resid 
ual  gas  did  not  support  life,  he  called  it  "noxious/'  or  injurious,  air 
He  did  not  realize,  however,  that  his  "noxious  air,"  or  nitrogen,  as  it  is 
now  called,  is  the  constituent  of  the  atmosphere  that  remains  after 
removal  of  the  oxygen  and  carbon  dioxide.  He  thought  that  the  "noxious 
air"  was  atmospheric  air  that  had  taken  up  phlogiston  from  the  substance 
that  had  been  burned.  According  to  Rutherford,  ".  .  .  this  conjecture  is 
confirmed  by  the  fact  that  air  which  has  served  for  the  calcination  of 
metals  is  similar,  and  has  clearly  taken  away  from  them  their  phlogiston." 
He  thought  that  the  "mephitic  air"  obtained  by  burning  carbonaceous 
material  contained  less  phlogiston  than  the  "noxious  air"  remaining  after 
combustion  of  phosphorus.  Rutherford's  epoch-making  thesis,  Dissertatio 
Inauguralis  de  Aere  fxo  dicto,  ant  mephitico,  is  preserved  in  the  British 

*The  Belgian  chemist  Jan  Baptist  van  Helmont  (1577-1 644  ^  had  shown^  that 
when  must  undergoes  fermentation  a  kind  of  air  which  he  called  '  gas  sylvestre  and 
which  is  identical  with  the  non-respirable  gas  given  off  by  burning  charcoal  escapes 
(70),  but  considered  it  a  transformation  product  of  water  (71).  He  was  the  first 
to  use  the  word  gas. 


Courtesy  H.  S,  van  Klooster 


Jan  Baptist  van  Helmont,  1577-1644.  Belgian  physician  and  chemist  who 
made  a  detailed  study  of  carbon  dioxide  (gas  sylvestre)  and  understood  its 
preparation  by  the  burning  of  charcoal  or  other  carbonaceous  organic  mate 
rial,  by  fermentation  of  beer  and  wine,  and  by  action  of  vinegar  on  shells 

and  limestone.     See  also  ref,   (86). 


208  DISCOVERY  OF  THE  ELEMENTS 

Museum  (12,  39)  and  at  the  University  of  Edinburgh  and  has  been 
translated  into  English. 

After  completing  his  medical  course,  Dr.  Rutherford  traveled  for 
three  years  in  England,  France,  and  Italy.  Upon  returning  to  Edinburgh 
in  1775  he  began  his  medical  practice,  and  never  again  engaged  in  chemi 
cal  research.  Eleven  years  later  he  accepted  the  chair  of  botany  at 
Edinburgh,  but  continued  to  practice  medicine,  He  sewed  for  a  time 
as  president  of  the  Royal  College  of  Physicians  of  Edinburgh.  Dr. 
Rutherford  had  a  pleasant  disposition,  and  displayed  true  loyalty  and 
friendship  toward  his  honored  teacher,  Dr.  Black  (12). 

Although  most  authorities  agree  that  Dr.  Rutherford  was  the  dis 
coverer  of  nitrogen,  it  would  be  unfair  to  disregard  the  work  of  Scheele, 
Cavendish,  and  Priestley.  Scheele  obtained  nitrogen  at  about  the  same 
time  by  absorbing  the  oxygen  of  the  atmosphere  in  liver  of  sulfur  or  a 
mixture  of  sulfur  and  iron  filings  (13).  One  of  Cavendish's  papers, 
written  before  1772  and  marked  in  his  handwriting  "communicated  to 
Dr.  Priestley,"  describes  his  method  of  preparing  "burnt  air"  by  passing 
atmospheric  air  repeatedly  aver  red-hot  charcoal,  and  then  removing 
the  carbon  dioxide  by  absorbing  it  in  caustic  potash.  He  studied  the 
properties  of  nitrogen  carefully,  as  shown  by  this  accurate  description: 
"The  specific  gravity  of  this  air  was  found  to  differ  very  little  from  that 
of  common  air;  of  the  two  it  seemed  rather  lighter.  It  extinguished  flame, 
and  rendered  common  air  unfit  for  making  bodies  burn  in  the  same 
manner  as  fixed  air,  but  in  a  less  degree,  as  a  candle  which  burnt  about 
80"  in  pure  common  air,  and  which  went  out  immediately  in  common 
air  mixed  with  6/58  of  fixed  air  burnt  about  26"  in  common  air  mixed  with 
the  same  portion  of  this  burnt  air"  (14).  It  is  probable  that  Rutherford 
was  unacquainted  with  Priestley's  earlier  work  on  nitrogen  (38,  39). 

The  elementary  nature  of  nitrogen  was  long  disputed  by  some 
chemists.  In  1840  J,  Lawrence  Smith  presented  a  thesis  for  the  doctorate 
entitled  "The  Compound  Nature  of  Nitrogen"  (66).  In  his  "Simple 
Bodies  of  Chemistry,"  David  Low,  as  late  as  1848,  expressed  a  belief  in 
the  compound  nature  of  nitrogen,  based  on  the  curious  reasoning  that, 
since  ammonia  is  derived  from  the  organic  kingdom,  it  must  contain 
carbon,  and  that  therefore  nitrogen  must  consist  of  carbon  and  oxygen 
(49). 

E.  T.  Allen  of  the  Geophysical  Laboratoiy  in  Washington,  D.  C,, 
considered  W.  F.  Hillebrand's  observation  that  nitrogen  is  an  essential 
constituent  of  uraninite  the  "first  discovery  of  that  element  in  the  primi 
tive  crust  of  the  earth"  (63). 


IMPORTANT  GASES 


209 


OXYGEN 

"When  Air's  pure  essence  joins  the  vital  flood, 

And  with  phosphoric  Acid  dyes  the  blood, 

Your  Virgin  Trains  the  transient  Heat  dispart., 

And  lead  the  soft  combustion  round  the  heart; 

Life's  holy  lamp  with  fires  successive  -feed, 

From  the  crown  d  forehead  to  the  prostrate  weed, 

From  Earth's  proud  realms  to  all  that  swim  or  sweep 

The  yielding  ether  or  tumultuous  deep. 

You  swell  the  bulb  beneath  the  heaving  lawn, 

Brood  the  live  seed,  unfold  the  bursting  spawn; 

Nurse  with  soft  lap,  and  warm  with  fragrant  breath 

The  embryon  panting  in  the  arms  of  Death, 

Youth's  vivid  eye  with  living  light  adorn, 

And  fire  the  rising  blush  of  Beauty's  golden  morn"  (50), 

Many  books  have  been  written  about  the  discovery  of  oxygen.  The 
Orientalist  Heinrich  Julius  Klaproth,  a  son  of  the  famous  German  chemist 
Martin  Heinrich  Klaproth,  found  a  reference  to  this  gas  in  a  Chinese 
book  written  by  Mao-Khoa  about  the  middle  of  the  eighth  century  after 


Leonardo  da  Vinci,  1452-1519.  (From 
a  drawing  in  red  chalk  by  himself.  In 
die  Royal  Library,  Turin.)  Italian  artist, 
sculptor,  anatomist,  and  scientist  of  the 
first  rank.  Pioneer  in  mechanics  and 
aeronautics.  The  first  European  to  rec 
ognize  that  the  atmosphere  contains  at 
least  two  constituents. 


From  Jean  Paul  Richt&fs  "Leonardo*3 


Christ.  Mao-Kh6a  believed  that  the  atmosphere  is  composed  of  two 
substances:  Yann,  or  complete  air  (nitrogen),  and  Yne,  or  incomplete  air 
(oxygen).  Ordinary  air  can  be  made  more  perfect  by  using  metals, 


210  DISCOVERY   OF  THE  ELEMENTS 

sulfur,  or  carbon  to  rob  it  of  part  of  its  Yne.  He  said  that  when  these 
substances  burn  in  air,  they  combine  with  Yne,  which,  according  to 
Mao-Khoa,  never  occurs  free,  but  is  present  in  certain  minerals  and  in 
saltpeter,  from  which  it  can  be  driven  out  by  heating  (15,  34}.  Signor 
Muccioli  (36),  however,  has  questioned  the  authenticity  of  this  Chinese 

manuscript. 

The  first  European  to  state  that  air  is  not  an  element  was  the 
versatile  artist-scientist,  Leonardo  da  Vinci  ( 1452-1519 ) .  Leonardo,  keen 
observer  that  he  was,  noticed  that  air  is  consumed  in  respiration  and 
combustion,  but  that  it  is  not  completely  consumed  (15,  35,  57).  He 
described  clearly  and  strikingly  the  intimate  relation  between  combustion 
and  respiration  in  the  words  "Where  flame  cannot  live  no  animal  that 
draws  breath  can  live"  (58). 

In  1630  Jean  Key  noticed  the  increase  of  weight  of  tin  on  calcination, 
and  believed  that  it  "comes  from  the  air,  which  in  the  vessel  has  been 
rendered  denser,  heavier,  and  in  some  measure  adhesive,  by  the  vehe 
ment  and  long-continued  heat  of  the  furnace:  which  air  mixes  with  the 
cak  .  .  .  and  becomes  attached  to  its  most  minute  particles:  not  otherwise 
than  water  makes  heavier  sand  which  you  throw  into  it  and  agitate,  by 
moistening  it  and  adhering  to  the  smallest  of  its  grains"  (82,  83,  84,  85). 

In  1756  the  great  Russian  chemist  and  poet  M.  V.  Lomonosov  heated 
metals  in  airtight  sealed  glass  vessels  and  found  that  without  the  ad 
mission  of  outside  air  the  weight  of  the  metal  remained  constant  (87), 
He  concluded  that  the  increase  in  weight  of  a  metal  on  calcination  is 
caused  by  its  combination  with  the  air.  He  denied  the  existence  of 
phlogiston,  for  since  the  sealed  retoit  containing  the  metal  did  not  change 
weight  when  heated,  the  metal  could  not  have  lost  phlogiston.  These 
quantitative  experiments  of  Lomonosov  were  not  published  however 
but  were  preserved  in  the  archives  of  the  Academy  of  Sciences  of  St. 
Petersburg.  When  Lavoisier  made  similar  experiments  about  eighteen 
years  later  and  obtained  the  same  results,  he  observed  that  only  part 
of  the  air  in  the  sealed  retort  united  with  the  metal,  hence  that  air  is 
composed  of  two  gases  (87,  88). 

Robert  Hooke  (16),  in  his  famous  book  "Micro graphia"  published  in 
1665,  gave  a  complete  theory  of  combustion.  He  thought  that  air  con 
tains  a  substance  (oxygen)  that  exists  in  solid  form  in  saltpeter,  and 
a  larger  quantity  of  an  inert  substance  (nitrogen).  Dr.  John  Mayow, 
when  only  thirty-three  years  of  age,  explained  combustion  by  saying 
that  air  contains  a  Spiritus  nitro-aereus  (oxygen),  a  gas  that  is  con 
sumed  in  respiration  and  burning,  with  the  result  that  substances  no 
longer  burn  in  the  air  that  is  left.  He  thought  that  his  Spiritus  was  pres 
ent  in  saltpeter,  and  stated  that  it  existed,  not  in  the  alkaline  part  of 


THREE  IMPORTANT  GASES 


211 


the  salt,  but  in  the  acid  part.  According  to  Dr.  Mayow,  all  acids  contain 
the  Spiritus,  and  all  animals  absorb  it  into  their  blood  as  they  breathe 
(17).  T.  S.  Patterson,  however,  who  has  made  an  exhaustive  study  of 
Dr.  Mayow's  writings,  believes  that  his  contributions  to  the  theory  of 
combustion  have  been  greatly  over-estimated  (IS,  SO). 

The  first  person  to  prepare  oxygen  by  heating  saltpeter  was  Ole 
Borch,  but  he  did  not  know  how  to  collect  it  (19).  He  stated  in  1678 
that  it  did  not  burn  but  that  it  made  charcoal  burn  very  vigorously  (51 ). 
In  his  "Prominent  Danish  Scientists/'  V.  Meisen  shows  a  facsimile  of  the 
introduction  to  Borch's  "Nitrum  non  inflammari,"  which  was  published  in 
volume  five  of  Thomas  Bartholin's  "Acta  Medica:"  "In  a  little  book 
Naturalis  Historia  Nitri  (Authore  Guilielmo  Clarcke  Anglo,  Francofurti 
et  Hamburg  1675.8°.  p.  13),  a  man  of  learning  says:  "Saltpetre  is  ignitible, 
because  experience  shows  that  if  a  small  piece  of  it  is  cast  into  a  fire,  it 


From  GuntHer's  '"Early  Science  in  Oxford,"  Vol.  7 

Robert  Hooke's  Home,  Montague  House,  which  afterward  became  the  first 

home  of  the  British  Museum. 

is  ignited  at  once  and  burns,  leaving  a  rest  of  lime  or  ash.  It  -catches 
fire  suddenly  and  blazes  lively;  and  it  burns  downwards,  whereas  ordi 
narily  fire  always  burns  upwards/  In  numberless  experiments  I  have 
however  found  nothing  of  the  kind  ..."  (52).  William  Clarke's  "Treatise 
on  the  Natural  History  of  Nitre"  was  first  published  in  London  in  1670. 
A  Latin  translation  of  it  was  issued  in  1675.  Borch  was  a  great  physician, 


212 


DISCOVERY  OF  THE 


botanist,  chemist,  philologist,  and  historian  of  science  who  bequeathed  all 
his  property  to  the  University  of  Copenhagen  for  the  erection  and  mainte 
nance  of  Borch's  Collegium,  a  dormitory  for  students  deserving  of  financial 
aid  (52).  Stephen  Hales  also  prepared  oxygen  from  saltpeter  and 
collected  it  over  water,  but  thought  he  had  ordinary  air;  he  did  not  be 
lieve  in  the  existence  of  a  "vivifying  spirit"  in  the  atmosphere  (19) . 

In  April  1774,  there  appeared  in  Abbe  Rozier's  Journal  de  Physique 
a  remaikable  paper  by  Pierre  Bayen,  a  pharmacist  who  later  became  a 
medical  inspector  in  the  armies  of  the  French  Republic.  In  discussing 
his  experiments  with  mercuric  oxide,  Bayen  stated  that,  when  mercury  is 


John  Mayow,  1641-1679,  Eng 
lish  chemist  and  physician,  who 
died  quite  young.  Famous  for 
his  early  researches  on  com 
bustion  and  respiration  His 
theory  of  combustion  was  de 
scribed  in  his  tract  entitled  "De 
Sale  Nitro  et  Spirito  Nitro- 
aereo"  in  1674  (48). 


Courtesy  E.  R  Rtegel 


calcined,  it  does  not  lose  phlogiston,  but  combines  with  a  gas  and  in 
creases  in  weight.  He  thus  rejected  the  phlogiston  theory  three  years 
before  it  was  proved  false  by  Lavoisier  (-20). 

Bayen,  however,  like  all  his  predecessors  who  had  handled  oxygen, 
neglected  to  make  a  thorough  study  of  its  properties  and  failed  to  recog- 


THREE  IMPORTANT  GASES  213 


Title  Page  of  Bayen's 
"Opuscules  Chimiques" 


OPUSCULES 

CHIMIQUES 


r>  r. 


PIERRE     B   A  Y  E  JST  , 


r*    r?e   PXmtitut  n 
$  dc  la  Sncitttt*  dc 
e?  du  tv//t'w  de  Pharmacia  de  Paris 
lyun    dc$    Iti$pc<  tciirs    {r&wraitzc 
Service  d&  S&tit£  fifes  s£r?n£e$  de 


T  O    M   £      SECOND. 


A      PARIS, 

A.    J.    DUGOUR   £T    DURAND, 
Libraires,  Kuo  et  I16tel  Serpence, 


VI     D 


nize  it  as  a  new  substance.  As  Patterson  says,  he  ".  .  cannot  therefore 
be  regarded  as  having  discovered  it,  and  this  applies  with  greater  farce 
to  other  unconscious  preparations  of  oxygen  by  Hales  and  possibly  by 
Robert  Boyle,  and,  of  course,  still  more  strongly  to  the  vague  speculations 
of  Hooke  and  Mayow"  (18). 

Most  chemists  agree  that  the  actual  discovery  of  oxygen  was  made 
independently  at  about  the  same  time  by  Priestley  in  England  and 
Scheele  in  Sweden.  Priestley's  results,  to  be  sure,  were  published  before 
those  of  Scheele,  but  Scheele's  publisher  had  been  inexcusably  negligent 
The  question  of  priority  is  discussed  in  a  thorough  manner  in  Dr.  S.  M. 
Jorgensen's  book,  "Die  Entdeckung  des  Sauerstoffes,"  which  was  translated 
from  Danish  into  German  by  V.  Ortwed  and  Max  Speter.  The  general 
problem  of  duplication  in  the  history  of  chemical  discoveries  was  ably 
presented  by  Dr.  Paul  Walden  in  the  Journal  of  Chemical  Education  (59). 


214  DISCOVERY   OF  THE  ELEMENTS 

Joseph  Priestley  was  born  in  Fieldhead,  a  tiny  hamlet  near  Leeds,  on 
March  13  (old  style),  1733,  and  was  therefore  about  one  and  one-half 
years  older  than  that  other  great  pioneer  in  pneumatic  chemistry,  Mr. 
Heniy  Cavendish.  Although  Priestley  and  Cavendish  had  similar  sci 
entific  interests,  their  lives  and  personalities  offered  the  greatest  possible 
contrast.  Since  Priestley's  mother  died  when  he  was  only  six  years  old, 
he  was  entrusted  to  the  care  of  an  aunt,  Mrs.  Keighley,  of  whom  he 
afterward  said  that  she  "knew  no  other  use  of  wealth,  or  of  talents  of 
any  kind,  than  to  do  good"  (21). 

At  the  age  of  nineteen  years  he  was  sent  to  the  Dissenting  Academy 
at  Daventry  to  be  educated  for  the  liberal  ministry.  After  completing 
the  three-year  course,  he  ministered  to  congregations  at  Needham  Market 
and  later  at  Nantwich,  but  with  small  success.  In  1761  he  received  an 
appointment  as  teacher  of  languages  in  the  Dissenting  Academy  at 
Warrington,  and  taught  Latin,  Greek,  French,  Italian,  oratory,  and  civil 
law,  Although  these  subjects  were  only  distantly  related  to  the  science 
in  which  he  later  won  undying  fame,  Priestley  s  scientific  spirit  manifested 
itself  even  here-he  encouraged  absolute  freedom  of  speech  among  his 

students. 

Even  when  struggling  with  poverty  at  Nantwich,  Priestley  loved  to 
make  experiments;  and  from  his  meager  salary  he  purchased  an  air-pump 
and  an  electrical  machine.  In  about  1766  an  event  occurred  that  caused 
him  to  devote  the  rest  of  his  life  to  scientific  research,  namely  his  intro 
duction  to  the  great  American  statesman  and  scientist  Benjamin  Franklin, 
In  a  visit  to  London  Priestley  mentioned  to  Franklin  his  intention  of 
writing  a  history  of  electricity,  provided  the  necessary  books  could  be 
obtained.  "This  he  readily  undertook,"  Priestley  wrote  in  section  80  of 
his  Memoirs,  "and  my  friends  assisting  him  in  it,  I  set  about  the  work, 
without  having  the  least  idea  of  doing  anything  more  than  writing  a 
distinct  and  methodical  account  of  all  that  had  been  done  by  others" 
(79;.  In  the  course  of  this  purely  literary  endeavor  Priestley  made 
some  original  experiments  with  his  electrical  machine  in  order  to  settle 
disputed  points  (67). 

Not  long  after  this  meeting  with  Benjamin  Franklin,  Priestley  ac 
cepted  a  pastorate  at  Leeds.  Since  the  parsonage  happened  to  be 
located  next  door  to  the  Jakes  and  Nell  Brewery,  the  Reverend  Mr. 
Priestley  had  a  convenient  source  of  "fixed  air"  for  his  experiments.  He 
soon  discovered  the  pleasant  taste  of  water  charged  with  this  gas,  and 
recommended  the  refreshing  beverage  to  his  friends.  Dr,  William  Brown- 
rigg  had  previously  made  the  same  discovery  (22,  47), 

Since  Priestley  found  that  some  gases  can  be  collected  over  water 
while  others  require  mercury  (41),  he  concluded  that  there  must  be 
different  kinds  of  "airs."  On  August  1,  1774,  he  heated  mercuric  oxide 


THREE  IMPORTANT   GASES  215 


The  Stuart  Portrait  of  Joseph  Priestley,  1733-1804 

"Oh  what  an  active  brain  had  he, 
And  clear  discriminating  mind. 

Through  life  his  great  desire  was  this: 
To  bless  and  elevate  mankind" (54) . 


216 


DISCOVERY   OF  THE  ELEMENTS 


with  a  burning  glass,  liberated  a  gas,  "dephlogisticated  air"  (oxygen), 
and  collected  it  over  water.  In  an  atmosphere  of  this  gas,  substances 
burned  more  biilliantly  than  in  air.  Five  years  later  he  tested  the  respir- 
ability  of  his  "dephlogisticated  air"  by  mixing  it  with  nitric  oxide  ovei 


TO    TUR    RIGHT   HONOURABLE 

THE  EARL  OF  S  K  E  L  B  UHR  N  E, 

THIS    TREATISE   IS, 

WITH  THE  GREATEST  GRATITUDE* 

AND     RESPECT, 

INSCRIBED, 

BY    HIS    LORDSHIP** 
MOST  OBLIGED, 
AND    OBEDIENT    - 
HUMBLE  SERVANT, 

J.    P  R  I  E  S  T  L  E  Y. 


Dedication  of  Priestley's  "Ex 
periments    and    Observations 
on    Diffeient    Kinds    of   Air," 
1774. 


water.  He  found  that  much  more  nitric  oxide  was  required  to  render 
a  given  volume  of  "dephlogisticated  air"  unfit  for  a  mouse  to  breathe  than 
for  an  equal  volume  of  atmospheric  air.  His  description  of  the  experi 
ment  is  charmingly  naive: 

My  readei  will  not  wonder  that,  after  having  ascertained  the  superior 
goodness  of  dephlogisticated  air  by  mice  living  in  it,  and  the  other  tests  above 
mentioned,  I  should  have  the  curiosity  to  taste  it  myself.  I  have  gratified  that 
curiosity  by  bieathing  it,  drawing  it  through  a  glass  syphon,  and  by  this  means 
I  reduced  a  laige  jar  full  of  it  to  the  standard  of  common  air.  The  feeling  of  it 
to  my  lungs  was  not  sensibly  different  fiom  that  of  common  air,  but  I  fancied! 
that  my  bieast  felt  peculiarly  light  and  easy  foi  some  time  afterwards.  Who  can 
tell  but  that,  in  time,  this  pure  air  may  become  a  fashionable  article  in  luxury? 
Hitherto  only  two  mice  and  myself  have  had  the  privilege  of  breathing  it  (24) , 


THREE   IMPORTANT   GASES  217 


From  Priestley's  "Experiments  and  Observations  on  Different  Kinds  of  Air"  1774  and  1790 

See  references  (9)  and  (22) 

Priestley's  Apparatus  for  Studying  the  Composition  of  the  Atmosphere.  Fig. 
1,  a,  Earthenware  pneumatic  trough,  8"  deep;  bb,  flat  stones,  which  in  his 
later  wooden  trough  were  replaced  by  a  shelf  for  holding  the  jars;  cc,  jars, 
10"  X  2Va",  for  collecting  gases;  d,  tall  beer  glass  containing  enough  air  to 
sustain  a  mouse  for  from  20  to  30  minutes,  and  "something  on  which  it  may 
conveniently  sit,  out  of  reach  of  the  water."  The  mouse  was  introduced  by 
passing  it  quickly  through  the  water;  e,  gas  generator  heated  by  a  candle 
or  a  red-hot  poker.  Fig.  2,  "Pots  and  tea-dishes"  to  slide  under  the  gas-filled 
jars  when  removing  them  from  the  trough.  Fig.  3,  Receiver  for  keeping  the 
mice  alive.  It  was  open  at  top  and  bottom,  except  for  plates  of  perforated 
tin,  the  lower  of  which  stood  on  a  wooden  frame  to  permit  circulation  of  air. 
To  avoid  chilling  the  mice,  this  receiver  was  kept  on  a  shelf  over  the  kitchen 
fireplace*  Fig.  4,  Cork  for  closing  a  phial  of  solid  or  liquid  which  must  be 
transferred,  without  wetting  the  contents,  to  a  jar  of  gas  in  the  pneumatic 
trough.  Fig.  5,  Wire  stand  for  supporting  a  gallipot  inside  a  jar  of  gas. 
Fig.  6,  Funnel  for  "pouring  air"  into  a  glass  jar  by  displacement  of  water. 
Fig.  11,  Glass  cylinder  for  admitting  a  candle  to  test  the  ability  of  the  gas  to 
support  combustion.  Fig.  12,  a,  Wax  candle,  bent  for  introducing  it  into  a 
vessel,  with  the  flame  upward;  b,  wire;  c,  candle  to  be  held  under  a  jar 
standing  in  water.  It  was  removed  the  instant  the  flame  was  extinguished,  to 
avoid  contamination  of  the  gas  in  the  jar  with  smoke. 


218  DISCOVERY   OF  THE  ELEMENTS 

In  the  preface  to  the  1790  edition  of  his  "Experiments  and  Observa 
tions  on  Different  Kinds  of  Air"  Priestley  wrote:  "And  it  will  not  now  be 
thought  very  assuming  to  say,  that,  by  working  in  a  tub  of  water,  or  a 
bason  of  quicksilver,  we  may  perhaps  discover  principles  of  more  ex 
tensive  influence  than  even  that  of  gravity  itself  .  .  ."  (68). 

Inspired  by  Priestley's  illuminating  experiments  with  oxygen,  carbon 
dioxide,  and  other  gases,  the  great  Spanish  physicist,  historian,  and  poet, 
Father  Jose  de  Viera  y  Clavijo  (1738-1799),  praised  him  in  a  long  poem. 
Although  the  following  prose  translation  of  an  excerpt  from  it  cannot 
render  justice  to  the  poetry,  it  nevertheless  illustrates  an  early  intellectual 
bond  between  the  scientists  of  Spain,  Italy,  England,  and  the  United 
States  of  America. 

"If  by  His  mandate  Torricelli 

Poised  air's  vast  sea  in  slender  tube, 

Newton  with  his  wondrous  prism 

Dawn's  seven  rays  dissected  out, 

Jove's  thunder  and  Heavens  ether 

Yielded  to  Franklins  rod, 

God  also  guided  Priestley  when  He  said: 

Take  thou  this  earth,  take  from  it  the  fixed  air"  (53).* 

From  1772  to  1779  Priestley  served  as  literary  companion  to  Lord 
Shelburne.  His  most  important  chemical  experiments,  culminating  in 
the  discovery  of  oxygen,  were  made  during  this  period,  and  his  book 
entitled  "Experiments  and  Observations  on  Different  Kinds  of  Air"  was 
therefore  affectionately  dedicated  to  Lord  Shelburne.  In  1780  Priestley 
became  minister  to  a  large  metropolitan  congregation  in  Birmingham. 
Here  he  was  contented  in  his  ministry  and  happy  in  his  association  with 
such  men  as  James  Watt,  Josiah  Wedgwood,  and  Erasmus  Darwin  at  the 
meetings  of  the  Lunar  Society,  which  met  on  the  first  Monday  evening 
after  each  full  moon  in  order  that  the  members  might  find  their  way 
home  through  the  unlighted  streets,  At  Birmingham  he  completed  his 
six-volume  work  on  "Different  Kinds  of  Air,"  which  was  later  abridged  to 
three  volumes. 

The  struggles  of  the  American  and  French  revolutionists  aroused 
Priestley's  sympathy,  and  he  was  no  dissembler.  On  July  14,  1791,  about 

*  Si  61  hizo  d  Torricelli  que  pesase 

En  tubo  estrecho  el  mar  de  la  atmosfera; 

Que  Newton  con  un  prisma  disecase 

Los  siete  rayos  de  la  luz  primera; 

Que  Franklin  con  su  barra  le  robase 

El  rayo  d  Jove,  el  Eter  d  la  esfera; 

Tambien  guid  d  Priestley,  quando  le  diw 

Toma  esa  tierra,  saca  el  Ayre  fixo  .  .  . "  ( 53 ) . 


THREE  IMPORTANT  GASES 


219 


Frontispiece  of  Priestley's  "Observations  on  Different  Kinds  of  Air"  1774  and  1790 

See  references  (9)  and  (22) 

Priestley's  Laboratory.  Fig.  7,  Apparatus  for  expelling  gas  from  solids.  Tlie 
fireplace  was  used  for  heating  a  gun  barrel  containing  dry  sand  which  had 
previously  been  ignited.  The  open  end  of  the  gun  barrel  was  luted  to  the 
stem  of  a  tobacco  pipe  leading  to  a  trough  of  mercury.  Fig.  85  a,  Trough 
containing  an  inverted  cylinder,  b,  of  mercury;  c,  a  phial  containing  sub 
stances  from  which  a  gas  may  be  liberated;  d,  glass  trap  to  intercept  moisture. 
Fig.  9,  Bladder  for  transferring  gases.  It  contained  a  bent  glass  tube  at  one 
end  and  at  the  other  a  one-hole  cork  to  admit  a  funnel.  After  the  gas  had 
been  admitted,  the  bladder  was  tied  tightly  with  string.  Fig.  10,  a,  Appara 
tus  for  impregnating  a  fluid  with  gas;  b,  bowl  containing  a  quantity  of  the 
same  fluid;  c,  phial  containing  chalk,  cream  of  tartar,  or  pearlash,  and  dilute 
sulfuric  acid  for  generating  carbon  dioxide;  dy  flexible  leather  tube,  which 
permitted  Priestley  to  shake  the  gas  generator,  c.  Fig.  13,  Siphon.  Fig.  14, 
Evacuated  bell  jar.  Fig.  15,  Apparatus  for  measuring  small  quantities  of  gas 
in  his  experiments  with  "nitrous  air"  (nitric  oxide),  a,  Small  glass  tube; 
Z?>  wire;  c,  sharply  bent,  thin  plate  of  iron  for  withdrawing  the  wire.  This 
little  apparatus  was  introduced  under  water  into  a  jar  of  nitric  oxide,  and 
when  the  wire  was  withdrawn,  nitric  oxide  took  its  place.  Priestley  meas 
ured  the  lengths  of  the  columns  of  air,  of  nitric  oxide,  and  of  the  resulting 
nitrogen  peroxide  after  admixture.  Fig.  16,  Apparatus  for  taking  the  electric 
spark  in  any  kind  of  gas.  a,  Mercury  column;  bs  brass  knob.  Figs.  17,  18, 
and  19  are  different  forms  of  apparatus  for  taking  the  electric  spark  in  gases. 
Fig,  19  represents  a  mercury-filled  siphon  containing  an  iron  wire,  aay  in 
each  leg.  Any  gas  which  was  introduced  would  rise  to  bb,  the  upper  part 
of  the  siphon.  The  mercury  basins  could  be  made  part  of  an  electric  circuit. 


220  DISCOVERY   OF  THE   ELEMENTS 

eighty  persons  had  a  dinner  at  a  Biimmgham  hotel  in  obseivance  of  the 
second  anniversary  of  the  fall  of  the  Bastille.  A  mob  shattered  the  win 
dows  with  stones.  Although  Priestley  did  not  attend  the  dinner,  his 
political  views  were  well  known  The  fanatics  broke  up  the  meeting  at 
the  hotel,  surged  through  the  streets  of  Birmingham,  burned  Priestley's 
church,  home,  and  hbiary,  and  shattered  his  apparatus.  Even  then 
their  thirst  for  violence  was  not  satiated,  and  furious  rioting  continued  for 
three  days,  Before  the  dragoons  were  at  last  able  to  disperse  the  mob 
and  restore  order,  the  homes  and  churches  of  many  dissenters  had  become 
charred  ruins  (23}. 

With  the  aid  of  friends,  the  Priestley  family  escaped  without  personal 
injury.  After  three  unhappy  years  m  London,  they  finally  succeeded  in 
collecting  a  small  indemnity  from  the  British  Government,  and  emigrated 
to  America  (23}.  In  the  first  volume  of  his  "Discourses  on  the  Evidence 
of  Revealed  Religion,"  in  the  dedication  to  his  successor  at  Hackney, 
the  Reverend  Thomas  Belsham,  Priestley  wrote  in  March,  1794:  "I  have 
no  where  known,  or  heard  of,  such  studious  and  orderly  young  men  as 
those  of  the  New  College  at  Hackney  ...  I  think  myself  peculiarly 
happy  in  leaving  my  congregation,  and  especially  my  classes  of  young 
persons,  under  your  care  .  .  .  Happy  shall  I  think  myself  if,  in  any  future 
destination,  I  can  find,  or  form,  a  sphere  of  exeition  of  a  similar  kind;  that 
I  may  be  in  America,  what  I  shall  leave  you  here  .  .  /'  (61). 

In  the  dedication  of  the  second  volume  of  these  "Discourses"  to 
John  Adams,  Vice-president  of  the  United  States,  Priestley  wrote  in  May, 
1796:  "It  is  happy  that,  in  this  country,  religion  has  no  connection  with 
civil  power,  a  circumstance  which  gives  the  cause  of  truth  all  the  ad 
vantage  that  its  best  friends  can  desire.  ...  I  cannot  conclude  this 
address  without  expressing  the  satisfaction  I  feel  in  the  government 
which  has  afforded  me  an  asylum  from  the  pei sedition  which  obliged  me 
to  leave  England,  persuaded  that,  its  principles  being  fundamentally 
good,  instead  of  tending,  like  the  old  governments  of  Europe,  to  greater 
abuse,  it  will  tend  to  continual  melioration.  Still,  however,  my  utmost 
wish  is  to  live  as  a  stranger  among  you,  with  liberty  to  attend  without 
interruption  to  my  favourite  pursuits;  wishing  well  to  my  native  country, 
as  I  do  to  all  the  world,  and  hoping  that  its  interest,  and  those  of  this 
country,  will  be  inseparable,  and  consequently  that  peace  between  them 
will  be  perpetual"  (61). 

In  1785,  nine  years  before  his  arrival  in  the  United  States,  Priestley 
had  been  elected  to  foreign  membership  in  the  American  Philosophical 
Society.  His  famous  chemical  researches  carried  out  in  England  were 
often  discussed  in  early  meetings  of  that  Society  (67),  After  his  arrival 
in  Pennsylvania  Priestley  participated  actively  in  the  affairs  of  the 


THREE   IMPORTANT   GASES  221 


From  Zekert's  "Carl  Wilhelm  Scheele.     Sein  Leben  und  seine  Werke" 
Stralsund,  the  Birthplace  of  Scheele* 

Society,  sometimes  attended  its  meetings,  and  "was  considered  for  presi 
dent  but  declined  in  favor  of  Mr.  [Thomas]  Jefferson"  (67).  Priestley's 
last  days  were  spent  in  the  peaceful  town  of  Northumberland,  Pennsyl 
vania,  where  he  worked  without  interference  at  his  beloved  experiments 
(33).  He  died  on  February  65  1804,  and  was  buried  in  the  Quaker 
cemetery  at  Northumberland. 

On  the  one  hundredth  anniversary  of  the  discovery  of  oxygen,  a  large 
audience  assembled  in  Birmingham  for  the  unveiling  of  a  statue  of  Joseph 
Priestley,  and  an  eloquent  eulogy  and  biographical  sketch  was  delivered 
by  Thomas  Huxley  (25).  At  the  same  time  the  scientists  of  Leeds 
assembled  at  Priestley's  birthplace  and  the  chemists  of  America  gathered 
at  his  grave  near  the  banks  of  the  Susquehanna  to  honor  his  memory  (26) . 
The  meeting  in  Pennsylvania  was  memorable  not  only  because  it  marked 
the  centennial  of  the  discovery  of  oxygen  but  also  because  it  resulted  in 
the  founding  of  the  American  Chemical  Society. 

Carl  Wilhelm  Scheele  was  born  on  December  9  (or  19),  1742,,  in 
Stralsund,  then  the  capital  of  Swedish  Pomerania.  The  discrepancy  in 
the  date  may  perhaps  be  explained  by  the  fact  that  at  that  time  the  Julian 
calendar  was  still  in  use  (72),  His  lineage  was  entirely  German,  as  is 
clearly  evident  from  the  genealogy  published  by  Professor  Otto  Zekert 
(73)  and  from  the  fact  that  Scheele  usually  wrote  in  German.  He  was 
the  seventh  child  in  a  family  of  eleven,  and,  since  the  family  was  not 
as  rich  in  worldly  goods  as  in  children,  he  was  apprenticed  at  the  agei 
of  fourteen  years  to  an  apothecary  named  Martin  Anders  Bauch,  owner 
of  the  Unicorn  Pharmacy  in  Gothenburg.  Like  other  pharmacists  of  his 
time,  Bauch  prepared  his  own  medicines  from  the  crude  drugs  and  was 
well  versed  in  chemistry.  In  his  laboratory  were  to  be  found  many  inor 
ganic  salts,  the  mineral  acids,  a  few  ores,  rock-crystal,  phosphorus,  sulfur, 

*  Reproduced  by  kind  permission  of  Mr.  Arthur  Nemayer,  Buchdruckerei  und  Verlag, 
Mittenwald,  Bavaria. 


222 


DISCOVERY  OF  THE  ELEMENTS 


benzole  acid,  and  camphor.  His  chemical  library  included  the  works  of 
H.  Boerhaave,  N.  Lemery,  J.  Kunckel,  and  Caspar  Neumann  (27).  The 
fourteen-year-old  apprentice  soon  developed  a  passion  for  reading  chemi 
cal  books  critically  and  repeating  the  experiments  described  in  them.  His 
memory  for  chemical  facts  was  so  great  that,  after  reading  a  book  through 
once  or  twice,  he  had  no  need  to  consult  it  again. 

After  working  and  studying  at  the  Unicorn  Pharmacy  for  eight  years 
Scheele  served  for  three  years  (1765-68)  as  clerk  at  the  Spotted  Eagle 
Pharmacy  at  Malmo,  which  was  owned  by  Peter  Magnus  Kjellstrom. 
There  he  met  the  famous  apothecary  and  chemist  Anders  Jahan  Retzius, 
who,  recognizing  young  Scheele's  genius  for  experimentation  in  physical 


Youthful  Portiait  of  Carl  Wilhelm 
Scheele,  1742-1786.*  Swedish 
pharmacist  and  chemist.  Independ 
ent  discoveier  of  oxygen.  He  dis 
covered  aisenic  acid,  distinguished 
between  nitric  and  nitrous  acids, 
demonstrated  the  presence  of  tar- 
tanc,  citric,  malic  and  gallic  acids 
in  plants,  and  discovered  lactic  and 
uric  acids  in  the  animal  realm. 


From  Zekert's  "C    W    Scheele 
Scin  Leben  und  seine  Weilte" 


science,  persuaded  him  to  keep  a  record  of  his  experiments,  Even  during 
the  Malmo  period  Scheele  was  engaged  in  the  isolation  and  investigation 
of  gases  (74}. 

From  1768  to  1770  he  served  as  clerk  at  the  Gilded  Raven  Pharmacy 
in  Stockholm,  which  was  owned  by  Johan  Scharenberg.  His  reason  for 
leaving  his  conscientious,  exacting  work  in  the  prescription  department 

*  Reproduced  by  kind  permission  of  Mr.  Arthur  Nemayer,  Buchdruckerei  und  Verlag, 
Mittenwald,  Bavaria. 


THREE  IMPORTANT  GASES  223 

there  was  that  it  left  him  no  time  for  experimentation.  He  always  con 
sidered  his  chemical  research  as  a  sideline  however  and  never  neglected 
his  duty  in  the  pharmacy  (75). 

Two  of  his  earliest  papers  were  rejected  by  the  Stockholm  Academy, 
possibly  because  of  the  unmethodical  style  in  which  they  were  written. 
The  editor  who  refused  them  was  Torbern  Bergman,  who  afterward 
became  Scheele's  lifelong  friend  (27).  In  1770  Scheele  accepted  a  posi 
tion  in  C.  L.  Lokk's  pharmacy,  the  Arms  of  Uppland,  at  Upsala.  One  day 
Lokk  noticed  that  saltpeter  which  has  been  fused  for  some  time  remains 
neutral,  but  evolves  red  fumes  when  treated  with  vinegar.  Assessor  Gahn? 
the  famous  mineralogist  who  discovered  manganese,  was  unable  to  explain 
the  change,  and  Bergman,  the  illustrious  professor  of  chemistry  at  Upsala, 
could  give  him  no  help.  Scheele,  however,  readily  explained  that  there 
are  two  "spirits  of  niter,"  or,  as  one  says  today,  two  acids,  nitric  and  nitrous. 

Gahn  and  Scheele  became  close  friends,  and  much  of  their  corre 
spondence  has  been  preserved.  It  was  through  Gahn  that  Scheele  made 
the  acquaintance  of  Bergman.  When  Scheele  explained  that  potassium 
nitrate  is  converted  by  fusion  into  the  deliquescent  salt,  potassium  nitrite, 
Bergman  became  deeply  interested  in  the  young  chemist,  and  they,  too, 
formed  a  lasting  friendship.  Bergman  received  much  of  his  practical 
instruction  from  Scheele,  while  Scheele's  intellectual  interests  were 
broadened  by  his  long  association  with  the  scholarly  Bergman  (27,  69), 

In  spite  of  many  offers  from  universities,  Scheele  never  exchanged 
the  practice  of  pharmacy  for  an  academic  career.  The  pharmacies  of  his 
day  were  quiet  centers  of  original  research,  and  as  Scheele  himself  once 
said  to  Assessor  Gahn,  "...  To  explain  new  phenomena,  that  is  my  task; 
and  how  happy  is  the  scientist  when  he  finds  what  he  so  diligently  sought, 
a  pleasure  that  gladdens  the  heart"  (28). 

His  most  brilliant  discoveries  were  made  at  the  Lokk  pharmacy. 
His  notebooks,  which  have  since  been  edited  and  published  by  Baron 
Nordenskiold,  show  that  he  prepared  oxygen  in  1771  and  1772,  that  is  to 
say,  at  least  two  years  before  Priestley  did.  Scheele  made  it  by  heating 
silver  carbonate,  mercuric  carbonate,  mercuric  oxide,  niter,  and  mag 
nesium  nitrate,  and  by  distilling  a  mixture  of  manganese  dioxide  and 
arsenic  acid.  When  oxygen  is  prepared  by  heating  silver  or  mercuric 
carbonate,  the  carbon  dioxide  must  be  absorbed  in  caustic  alkali. 

The  results  of  these  experiments  were  discussed  in  the  book,  "Fire 
and  Air,M  which  Scheele  sent  to  his  publisher,  Swederus,  near  the  end  of 
1775,  but  the  book  did  not  appear  until  1777.  In  August,  1776,  Scheele, 
exasperated  at  the  delay,  wrote  dejectedly  to  Bergman,  "I  have  thought 
for  some  time  back,  and  I  am  now  more  than  ever  convinced,  that  the 
greater  number  of  my  laborious  experiments  on  fire  will  be  repeated, 


224 


DISCOVERY  OF  THE  ELEMENTS 


possibly  in  a  somewhat  different  manner,  by  others,  and  that  their  work 
will  be  published  sooner  than  my  own,  which  is  concerned  also  with  air. 
It  will  then  be  said  that  my  experiments  are  taken,  it  may  be  in  a  slightly 
altered  form,  from  their  writings.  I  have  Swederus  to  thank  for  all  this" 
(29).  Scheele  s  discoveiy  of  oxygen  was  anticipated,  as  he  had  feared, 
but  he  is  universally  recognized  as  an  independent  discoverer  of  that  gas. 
When  the  English  edition  of  Scheele's  "Fire  and  Air"  appeared,  it 
was  provided  with  notes  by  English  chemists.  The  translator  Johann 
Remhold  Foister  mentioned  in  a  letter  to  Scheele  that  some  of  these 


'  /  ^ 


Sigfsmund  Friedrich  Hermbstadt,  1760- 
1833.  Professor  of  chemistry  and  phar 
macy  at  the  School  of  Medicine  and  Sur 
gery  m  Berlin,  later  professor  of  chemis 
try  and  technology  at  the  University  of 
Beilin,  He  was  one  of  the  first  chemists 
in  Germany  to  adopt  Lavoisier's  views  on 
combustion.  Author  of  books  on  dyeing, 
bleaching,  tanning,  soap-making,  and  beet 
sugar,  Editor  of  the  complete  works  of 
C.  W.  Scheele. 


Courts?]/    Edgar   Fahs    Smith 

chemists  had  disagreed  with  some  ot  his  conclusions.  Forster  added 
however:  "Your  adversaries  aie  people  who  do  not  lack  courtesy,  kind 
ness,  moral  character,  nor  knowledge;  hence  a  discussion,  nobly  carried 
on,  cannot  be  anything  but  useful  to  the  realm  of  truth"  (72). 

In  his  handsomely  illustrated  "Pictorial  Life  History  of  the  Apothe 
cary  Chemist  Carl  Wilhelm  Scheele"  Professor  George  Urdang,  Director 
of  the  American  Institute  of  the  History  of  Pharmacy,  wrote:  "The 
authority  which  Scheele  enjoyed  was  so  great,  and  his  honesty  and  simplic 
ity  of  character  so  obvious  and  disarming,  that  none  of  the  usual  scientific 
jealousies  and  quarrels  ever  touched  him"  (72). 

In  1776  Scheele  became  a  provisor  of  the  pharmacy  at  Koping,  a 
little  town  on  the  north  shore  of  Lake  Malar,  The  owner,  Heinrich  Pohl, 


THREE   IMPORTANT   GASES  225 

had  died,  leaving  the  shop  to  his  young  widow,  Instead  of  finding  the 
prosperous  business  he  had  expected,  Scheele  met  the  discouraging  task 
of  freeing  the  estate  from  heavy  debt  (27),  but  he  finally  placed  the 
business  on  a  sound  financial  basis  and  purchased  it  from  the  widow  Pohl. 
By  1782  his  name  was  known  to  all  European  scientists,  and  his  financial 
condition  permitted  him  to  build  a  new  home  and  a  well-equipped  labora 
tory.  One  of  his  sisters  and  Mrs,  Pohl  kept  house  for  him. 

The  last  years  of  his  life  were  filled  with  intense  suffering  from  rheu 
matism.  When  he  realized  that  death  was  near,  he  married  the  widow 
Pohl  in  oider  that  the  estate  which  he  had  struggled  so  hard  to  save  might 
return  to  her.  He  died  three  days  later  on  May  21,  1786?  at  the  age  of 
forty- three  years.  His  entire  life  had  been  devoted  to  chemistry,  and 
in  one  of  his  letters  to  Gahn  one  may  read,  "Diese  edel  Wissenschaft  1st 
mem  Auge'*  (30). 

A  scholarly  volume  of  Scheele's  manuscripts  from  1756  to  1777,  in 
which  many  gaps  were  filled  and  Scheele's  difficult  abbreviations  were 
interpreted,  was  published  by  C.  W.  Oseen  in  1942  ( 76 ) .  This  publication 
is  in  German,  the  language  in  which  Scheele  usually  wrote.  On  the  150th 
anniversary  of  Scheele's  death  Bengt  Hildebrand  published  in  Lychnos, 
the  annual  of  the  Swedish  History  of  Science  Society,  a  comprehensive 
review  of  the  vast  literature  devoted  to  Scheele  and  his  work  (77). 

Scheele  was  a  phlogistcnist  to  the  end  of  his  life,  and  thought  that 
phlogiston  was  similar  to  the  imponderable  ether  of  the  physicists  and 
that  hydrogen  was  a  compound  of  phlogiston  and  "matter  of  heat."  It 
has  been  shown  that  certain  seventeenth-century  chemists  were  ahead 
of  most  eighteenth- century  scientists  in  their  understanding  of  the  compo 
sition  of  the  atmosphere  and  the  nature  of  combustion  and  respiration. 
Even  the  three  men  who  had  contributed  most  toward  an  understanding 
of  the  atmosphere— namely.  Cavendish,  Priestley,  and  Scheele— clung  to 
the  end  of  their  days  to  the  outgrown  phlogiston  theory. 

The  great  French  scientist,  Lavoisier,  would  have  liked  very  much  to 
be  considered  an  independent  discoverer  of  oxygen,  but  he  himself  may 
have  felt  the  weakness  of  his  claim.  He  wrote  in  his  "Memoire  sur  1'Exist- 
ence  de  1'Air  dans  TAcide  Nitreux,"  read  on  April  20,  1776,  "Perhaps, 
strictly  speaking,  there  is  nothing  in  it  of  which  Mr.  Priestley  would  not  be 
able  to  claim  the  original  idea;  but  as  the  same  facts  have  conducted  us  to 
diametrically  opposite  results,  I  trust  that,  if  I  am  reproached  for  having 
borrowed  my  proofs  from  the  works  of  this  celebrated  philosopher,  my 
right  at  least  to  the  conclusions  will  not  be  contested"  (31).  In  his 
remarkable  paper  "On  the  Nature  of  the  Principle  That  Combines  with 
Metals  during  Their  Calcination  and  Increases  Their  Weight,"  which  he 
had  read  during  the  Easter  season  of  1775,  he  had  announced  that  this 
*  "This  noble  science  is  my  eye." 


226          DISCOVERY  OF  THE  ELEMENTS 


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THREE  IMPORTANT   GASES 


227 


principle  is  simply  "the  purest  and  most  salubrious  part  of  the  air;  so  that 
if  the  air  which  has  been  fixed  in  a  metallic  combination  again  becomes 
free,  it  reappears  in  a  condition  in  which  it  is  eminently  respirable  and 
better  adapted  than  the  air  of  the  atmosphere  to  support  inflammation 
and  the  combustion  of  substances"  (32). 

This  was  the  death  blow  to  the  phlogiston  theory  (56).    Although 
Lavoisier  discovered  no  elements  himself,  he  was  the  first  to  assert  that 


M.    and   Mme.    Lavoisier.      In 

1777  Lavoisier  gave  quantita 
tive  proof  of  the  incorrectness  of 
the  phlogiston  theory.  Shortly 
after  Priestley  and  Scheele  dis 
covered  oxygen,  Lavoisier  gave 
the  true  explanation  of  com 
bustion  and  respiration  Ber- 
thollet,  Guyton  de  Morveau, 
Fourcroy,  and  Klaproth  were 
among  the  first  to  accept  the 
new  views.  See  also  ref.  (60) 


From  Grimaux's  "Lavoisier" 
From  the  Painting  by  David 

oxygen  is  an  element.  Moreover,  his  correct  explanation  of  combustion 
so  revolutionized  the  entire  science  of  chemistry  that,  under  the  new 
stimulus,  many  new  elements  were  discovered  soon  after  his  tragic  death 
on  the  guillotine.  For  this  great  service  scientists  will  always  honor  the 
name  of  Antoine-Laurent  Lavoisier. 

Although  Lavoisier  completely  renounced  phlogiston  as  a  material 
substance,  he  nevertheless  retained  in  his  list  of  chemical  elements  two 
unweighable,  immaterial  ones— light  and  "caloric"— which  in  the  opinion 
of  Boris  N.  Menschutkin  "presented  an  unmistakable  likeness  to  the 
principle  phlogiston,  as  conceived  by  Stahl"  (78). 

Late  in  the  eighteenth  century,  while  the  number  of  adherents  to 
the  phlogiston  theory  was  dwindling  and  the  antiphlogistians  were  gain- 


228 


DISCOVERY   OF  THE   ELEMENTS 


ing  ground,  Vasilii  Vladimirovich  Petrov  of  the  Medico-Surgical  Academy 
of  St.  Petersburg,  Russia,  began  to  carry  out  some  decisive  experiments 
to  confirm  or  disprove  the  new  doctrine  of  combustion.  In  1797,  when 


A    Statue    of    Lavoisier    which 
formed  part  of  the  French  Ex 
hibit  at  the  San  Francisco  Ex 
position  in   1915. 


the  Medico-Surgical  Academy  leceived  an  important  consignment  of 
physical  apparatus,  he  set  out  to  answer  experimentally  the  following 
questions: 

'1.     Can  natural  combustible  bodies  burn  in  an  airless  place? 

"2.     Can  metallic  calces  be  formed  in  an  airless  place  or  not? 

"3,  Can  perfect  acids  [oxides],  resulting  from  the  oxidation  of 
simple  bodies,  be  obtained  in  an  airless  place  or  not? 

"4.  If  products  can  be  obtained  in  the  preceding  cases  in  an  airless 
place,  will  they  be  heavier  than  the  materials  used  in  the  experiments?" 

(78). 

Petrov  spent  several  years  on  these  experiments  and  published  the 
results  in  three  books  and  in  papers  between  1801  and  1812. 

When  he  focused  a  burning  glass  upon  natural  substances,  such  as 
wood,  cotton,  or  paper,  in  a  closed  glass  jar  from  which  the  air  had  been 
pumped  out,  they  emitted  smoke  but  no  flame.  To  make  certain  that  no 


THREE  IMPORTANT   GASES  229 

air  had  been  retained  in  the  pores  of  the  combustible  substances 
or  in  the  glass,  Petrov  carefully  measuied  the  quantity  of  pure  oxygen 
required  to  burn  an  equal  quantity  of  wood  in  a  cylinder  placed  in  a 
pneumatic  trough.  He  found  this  quantity  to  be  thousands  of  times  as 
gieat  as  the  amount  of  oxygen  retained  in  the  wood  or  in  the  jar.  He  even 
burned  dry  chips  of  wood  in  a  perfect  Torricellian  vacuum.  Since  all 
of  the  substances  that  he  had  burned  in  a  vacuum  contained  oxygen,  as 
shown  by  Lavoisiei,  Petrov's  experiments  lent  further  support  to  the  new 
theory  of  combustion. 

In  his  experiments  to  answer  his  second  and  third  questions  Petrov 
found  that  in  presence  of  warm  sunlight  phosphorus  will  bum  for  a  few 
seconds  in  the  imperfect  vacuum  produced  by  the  air  pump,  but  that 
m  a  perfect  Torricellian  vacuum  it  will  neither  burn  nor  glow.  He  also 
obseived  that  in  a  perfect  vacuum  neither  phosphorus  nor  sulfur  will  form 
an  oxide. 

Since  all  of  his  experiments  completely  confiimed  the  new  views  on 
combustion,  Petrov  and  the  Russian  chemists  of  his  time  were  all  anti- 
phlogistians  (78).  Since  Petrov's  papers  were  printed  only  in  Russian, 
his  woik  has  not  received  from  chemists  in  othei  parts  of  the  world  the 
attention  it  deserves. 

V  V.  Petrov  was  bom  in  the  town  of  Oboyan  ( Government  of  Kursk) 
in  1761.  He  was  the  son  of  a  priest  and  was  educated  in  the  theological 
college  of  Kharkov  and  at  the  Higher  Pedagogical  Institute  of  St.  Peters 
burg,  where  he  graduated  in  1788.  For  some  years  he  taught  mathe 
matics  and  physics  at  Barnaul,  Siberia,  and  later  in  St.  Petersburg.  Having 
been  elected  professor  of  mathematics  and  physics  at  the  newly  established 
Medico-Surgical  Academy  of  St.  Petersburg  in  1795,  he  assembled  "the 
richest  physical  cabinet  of  his  time  in  Russia"  (78).  He  continued  his 
experimental  work  and  meteorological  observations  until  the  time  of  his 
death  in  1834.  His  work  was  commemorated  some  years  ago  by  the 
Institute  of  the  History  of  Science  and  Technology  (Academy  of  Sciences, 

U.S.S.R.). 

i 

LITERATURE  CITED 

i 

(1)  BOYLE,  R.,  "Memoirs  for  a  General  History  of  the  Air,"  Shaw's  Abridgment 

of  Boyle's  Works,  Vol.  3,  1725,  p    61;  SIR  W.  RAMSAY,  "The  Gases  of  the 
Atmosphere,"  Macmillan  &  Co.,  London,  1915,  p    10. 

(2)  KOPP,  H  ,  "Geschichte  der  Cherme,"  part  3,  Vievveg  und  Sohn,  Braunschweig, 

1845,  pp.  260-1;  part  1,  p.  Ill,  R.  JAGNAUX,  "Histoire  de  la  Chimie,"  Vol.  lt 
Baudry  et  Cie.,  Pans,  1891,  pp.  385-6. 

(3)  WILSON,  G.,  "The  Life  of  the  Honourable  Henry  Cavendish  Including  Ab 

stracts  of  His  More  Important  Scientific  Papers,"  printed  for  the  Cavendish 
Society,  London,  1851,  p,  17. 


230  DISCOVERY  OF  THE  ELEMENTS 

(4)  "Biographic  Universelle,  Ancienne  et  Moderne,"  85  vols.,  Vol  7,   Michaud 

Freres,  Paris,  1813,  p   456.    Biographical  sketch  of  Cavendish  by  Biot, 

(5)  THOMSON,  THOMAS,  "History  of  Chemistry,"  Vol.   1,   Colburn  and  Bentley, 

London,  1830,  pp.  336-8. 

(6)  WILSON,  G.,  "The  Life  of  the  Honourable  Henry  Cavendish,"  ref.   (3),  pp. 

168-9. 

(7)  DAVY,  DR.  JOHN,  "Memoirs  of  the  Life  of  Sir  Humphry  Davy,  Bart.,"  Vol.  1, 

Longman,  Rees,  Orme,  Brown,  Green,  and  Longman,  London,  1836,  p.  221. 

(8)  WILSON,  G.,  "The  Life  of  the  Honourable  Henry  Cavendish,"  ref.   (3),  pp. 

163-4. 

(9)  Ibid.,  pp.  25-7,  Alembic  Club  Reprint  No.  3.     H,  CAVENDISH,  "Experiments 

on  Air,"  University  of  Chicago  Press,  Chicago,  1906,  pp.  13-25;  J.  PRIESTLEY, 
"Experiments  and  Observations  on  Different  Kinds  of  Air,"  Vol.  I,  Thomas 
Pearson,  Birmingham,  1790,  pp.  5  and  270,  T.  E.  THORPE,  "Scientific  Papers 
of  the  Honourable  Henry  Cavendish,  F.R.S.,"  Vol.  2,  University  Press,  Cam 
bridge,  1921,  pp.  9-10,  H.  CAVENDISH,  Phil  Trans.,  74,  119-53  (1784). 
(JO)  WILSON,  G,  "The  Life  of  the  Honourable  Henry  Cavendish,"  ref  (3),  pp. 
182-5. 

(11)  RAMSAY,  SIR  W.,  "Life  and  Letters  of  Joseph  Black,  M.D.,"  Constable  and  Co., 

London,  1918,  p.  51. 

(12)  RAMSAY,  Sm  W ,  "The  Gases  of  the  Atmosphere,"  ref.  (1 ),  pp.  61-7, 

(13)  JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  ref.  (2),  Vol.  1,  p.  550;  Alembic  Club 

Reprint  No.  3.    H.  CAVENDISH,  "Experiments  on  Air,"  ref.  (9),  pp.  26-7,  C 
W.  SCHEELE,  "Sammtliche  physische  und  chermsche  Werke,"  translated  into 
German  by  Hermbstadt,  Vol,  1,  zweite  unveranderte  Auflage,  Mayer  and 
Miiller,  Berlin,  1891,  pp.  186-7. 

(14)  WILSON,  G.,  "The  Life  of  the  Honourable  Henry  Cavendish,"  ref.  (3),  p.  28, 

British  Assoc.  Report,  1839,  pp.  64-5;  Alembic  Club  Reprint  No.  3.  H 
CAVENDISH,  "Experiments  on  Air,"  ref.  (9),  p  49;  H.  CAVENDISH,  Phil 
Trans.,  75,  372-84  (1785). 

(15)  JORGENSEN,  S,  M.,  "Die  Entdeckung  des  Sauerstoffes,"  translated  from  Danish 

into  German  by  Ortwed  and  Speter.  Ferdinand  Enke,  Stuttgart,  1909,  pp 
3-11. 

(16)  Alembic  Club  Reprint  No    5,  "Extracts  from  Micrographia,"  University  of 

Chicago  Press,  Chicago,  1902,  pp.  43-7. 

(17)  JORGENSEN,  S.^  M.,  "Die  Entdeckung  des  Sauerstoffes,"  ref.    (15),  pp.  8-9; 

E.  RTEGEL,  "Four  eminent  chemists  who  died  before  their  time,"  /.  Chem. 
Educ.,  3,  1103-5  (Oct.,  1926). 

(18)  PATTERSON,  T.  S.,  "John  Mayow— in  contemporary  setting,"  Isis,  15  [3],  539 

(Sept.,  1931). 

(19)  JORGENSEN,  S.  M  ,  "Die  Entdeckung  des  Sauerstoffes,"  ref.  (15),  pp.  12-14. 

(20)  JORGENSEN,  S.  M,  "Die  Entdeckung  des  Sauerstoffes,"  ref,  (15),  pp.  30-3;  P. 

BAYEN,  Roziers  Jour,  de  Physique,  3,  285  (Apr.,  1774);  P.  BAYEN,  "Opus 
cules  Chimiques,"  Vol.  1,  Dugour  et  Durand,  Paris,  An  VI  de  la  Repubhque, 
p.  li  (:£loge  by  Parmentier),  ibid.,  p.  228. 

(21)  THORPE,  T.  E,?  "Essays  in  Historical  Chemistry,"  Macmillan  &  Co.,  London 

1894,  p.  30. 

(22)  PRIESTLEY,  J,  "Experiments  and  Observations  on  Different  Kinds  of  Air,"  J. 

Johnson,  London,  1774,  pp.  25-34. 

(23)  THORPE,  T.  E.,  "Essays  in  Historical  Chemistry,"  ref.  (21),  pp.  34-5. 

(24)  JAGNAUX,  R,  "Histoire  de  la  Chraue,"  ref    (2),  Vol    1,  p.  389;  J.  PRIESTLEY, 

"Experiments  and  Observations  on  Different  Kinds  of  Air,"  Vol.  2,  Thomas 
Pearson,  Birmingham,  1790,  pp.  161-2.  See  also,  ibid.,  pp.  102-87. 

(25)  HUXLEY,  T.,  "Science  and  Education.     Essays,"  D.  Appleton  &  Co    New  York 

City,  1897,  pp.  1-37. 


THEEE  IMPORTANT   GASES  231 

(26)  THORPE,  T.  E.,  "Essays  in  Historical  Chemistry/'  ref.  (21),  p.  28. 

(27)  Ibid.,  pp   56-65. 

(28)  SCHEELE,  C.  W.,  "Nachgelassene  Brief e  und  Aufzeichnungen/'  edited  by  Nor- 

denskiold,  Norstedt  &  Soner,  Stockholm,  1892,  p.  151     Letter  of  Scheele  to 
Gahn,  Dec.  26,  1774. 

(29)  Ibid.,$.  264. 

(30)  Ibid,  p   165. 

(31 )  "Oeuvres  de  Lavoisier,"  Vol.  2,  Imprimerie  Imperiale,  Paris,  1862?  p.  130. 

(32)  Ibid.,  Vol.  2,  p   127,  GRTMAUX,  ref    (S3),  p.  108. 

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232  DISCOVERY   OF  THE  ELEMENTS 

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(73)  ZEKERT,  OTTO,  "Carl  Wilhelm  Scheele     Sem  Leben  und  seine  Werke,"  Part  1, 

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THREE  IMPORTANT  GASES     233 

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( 78 )  MENSCHUTKIN,  B    N  ,  "Vasihi  Vladimirovich  Petrov  and  his  physico chemical 

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J   Chem   Educ,  25,  31-4  (Jan.,  1948) 

( 82 )  REY,  JEAN,  "The  Increase  in  Weight  of  Tin  and  Lead,"  Alembic  Club  Reprint 

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(84}     "Encyclopedic  methodique     Chimie  et  metallurgie,"  Vol.  4,  H.  Agasse,  Paris, 

1805  (An  XIII),  pp.  244-5 

(85)  McKiE,   D.,   "Antorne  Lavoisier.     The   Father  of  Modern   Chemistry,"  J.   B. 

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(July,  1947). 

(87)  MENSHUTKTN,  B.  N  ,  "Russia's  Lomonosov,"  Princeton  University  Press,  Prince 

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(88)  SPETER,  MAX,  ref    (42},  pp.  52-5      Chapter  on  M   V.  Lomonosov. 


From  Ramsay's  "The  Gases 
of  the  Atmosphere" 

Daniel  Rutherford,  1749-1819.    Scottish  physician,  botanist,  and 

chemist.    Discoverer  of  nitrogen.    Professor  of  botany  at  Edinburgh. 

President  of  the  Royal  College  of  Physicians  of  Edinburgh. 


.  .  .  Prosecuting  medical  studies  at  the  University 
of  Edinburgh,  he  early  discovered  the  existence  of  a 
gaseous  fluid,  now  known  as  nitrogen  gas  .  .  .  (I). 


8 


Rutherford,  discoverer  of  nitrogen 


Although  the  statement  that  nitrogen  was  discovered  in  1772 
by  Daniel  Rutherford  appears  in  most  histories  of  chemistry,  this 
Scottish  scientist  has  remained  almost  unknown  to  chemists. 
Nevertheless,  the  life  story  and  personal  character  of  Dr.  Ruther 
ford  emerge  from  the  correspondence  of  his  distinguished 
nephew,  Sir  Walter  Scott,  in  a  most  pleasing  manner.  Both  Dr. 
Rutherford  and  his  father  served  as  physicians  to  the  Scott  family, 
and  the  great  novelist's  allusions  to  them  combine  admiration, 
sincere  affection,  and  pardonable  family  pride. 


D 


r.  Rutherford  served  as  professor  of  botany  at  the  University 
of  Edinburgh  from  1786  to  1819,  and  was  thus  contemporary  with  Joseph 
Black,  Charles  Hope,  and  John  Robison.  He  invented  an  ingenious  maxi 
mum  and  minimum  thermometer  which,  is  described  in  many  modern  text 
books  of  physics.  The  tragic  circumstances  surrounding  his  sudden  death 
were  described  by  Sir  Walter  in  numerous  letters  to  members  of  his  family. 

In  his  doctor's  thesis  Rutherford  made  a  clear  distinction  between 
nitrogen  and  carbon  dioxide  which  most  of  his  contemporaries  had  failed 
to  observe.  Henry  Cavendish,  however,  had  made  this  distinction  some 
what  earlier,  but  had  failed  to  publish  his  results.  The  names  of  Priestley 
and  Scheele  are  also  intimately  connected  with  the  discovery  of  nitrogen. 

The  correspondence  of  Sir  Walter  Scott,  his  family  genealogy,  and 
the  ten-volume  biography  by  his  son-in-law,  J.  G.  Lockhart,  contain  fre 
quent  allusions  to  Scott's  grandfather,  Dr.  John  Rutherford,  one  of  the 
founders  of  the  medical  school  at  the  University  of  Edinburgh,  and  to  his 
uncle,  Dr.  Daniel  Rutherford,  who  is  usually  regarded  as  the  discoverer 
of  the  element  nitrogen.  In  the  genealogy  of  the  Scott  family  one  may 
read: 

By  his  first  wife,  Jean  Swinton,  Professor  John  Rutherford  had  a  son,  John, 
who  died  young,  and  a  daughter  Anne,  who  married*  Walter  Scott,  writer  to 
the  Signet,  and  became  the  mother  of  Sir  Walter  Scott  Bart.  He  married,  sec 
ondly,  on  'the  9th  August,  1743,  Anne  M'Kay,  by  whom  he  had  five  sons  and 
three  daughters.  .  .  .  Daniel  Rutherford,  second  son  of  Professor  John  Ruther- 

*  A  facsimile  of  the  marriage  contract  is  to  be  found  in  ret  (4), 

235 


236  DISCOVERY   OF  THE  ELEMENTS 

foid,  was  born  on  3rd  November,  1749.  Prosecuting  medical  studies  at  the 
Univeisity  of  Edinburgh,  he  early  discovered  the  existence  of  a  gaseous  fluid, 
now  known  as  nitrogen  gas  .  .  .  ( 1 ) . 

Sir  Walter  Scott  gave  some  of  the  same  facts  in  the  following  passage 
from  his  autobiography: 

In  [April,  1758]  my  father  marued  Anne  Rutherford,  eldest  daughter  of 
John  Rutherford^professor  of  medicine  in  the  University  of  Edinburgh.  He 
was  one  of  those  pupils  of  Boerhaave  to  whom  the  school  of  medicine  in  our 
noithern  metropolis  owes  its  rise,  and  a  man  distinguished  for  professional 
talent,  for  lively  wit,  and  for  literary  acquirements  Dr  Rutherford  was  twice 
married,  His  first  wife,  of  whom  my  mother  is  the  sole  surviving  child,  was  a 
daughter  of  Sir  John  Swmton  of  Swinton,  a  family  which  produced  many  dis 
tinguished  warriors  during  the  middle  ages,  and  which,  for  antiquity  and 
honourable  alliances,  may  rank  with  any  in  Britain  My  grandfather's  second 
wife  was  Miss  Mackay,  by  whom  he  had  a  second  family,  of  whom  are  now 
[1808]  alive,  Dr,  Daniel  Rutherford,  professor  of  'botany  in  the  University  of 
Edinburgh,  and  Misses  Janet  and  Christian  Rutherford,  amiable  and  accom 
plished  women  .  ,  .  (2)* 

As  might  be  expected,  the  Rutherfords,  both  father  and  son,  served 
as  physicians  to  the  Scott  family,  When  Sir  Walter  was  only  eighteen 
months  old,  his  right  leg  became  paralyzed,  and,  after  the  best  physicians 
had  failed  in  their  attempts  to  restore  the  use  of  it,  his  grandfather,  Dr. 
John  Rutherford,  had  him  sent  to  live  in  the  country  (3,  4).  During  a 
serious  illness  in  later  life,  Scott  "submitted  without  a  murmur  to  the 
severe  discipline  prescribed  by  his  affectionate  physician  [Dr.  Daniel] 
Rutherford  .  .  ."  (5). 

John  Rutherford  was  bom  in  the  Manse  of  Yarrow,  Scotland,  on 
August  1,  1695,  was  educated  at  the  grammar  school  at  Selkirk,  and 
studied  anatomy,  surgery,  and  materia  medica  in  London  and  later  in 
Leyden  under  Herman  Boerhaave.  After  receiving  his  medical  degree 
from  the  University  of  Reims  in  1719,  he  went  to  Edinburgh  to  engage  in 
private  practice.  In  November,  1724,  he  applied,  with  three  other  mem 
bers  of  the  College  of  Physicians,  for  the  keeping  of  the  college  garden, 
which  had  fallen  into  disuse.  With  the  consent  of  the  town  council,  the 
four  physicians  raised  medicinal  plants  there  and,  in  order  to  prepare 
drugs  for  the  apothecaries'  shops,  set  up  a  chemical  laboratory  at  their 
own  expense  Two  years  later  Dr.  Rutherford  was  appointed  Professor 
of  the  Practice  of  Medicine  in  the  medical  school  which  he  had  helped  to 
found.  He  used  Boerhaave's  "Aphorismi  de  Cognoscendis  et  Curandis 
Morbis"  as  a  textbook,  and  for  many  years  delivered  clinical  lectures  in 
the  Edinburgh  Infirmary,  He  resigned  in  1765,  and  died  in  1779  at  the 
age  of  eight-four  years  (6,7). 


RUTHERFOLD,  DISCOVER  OF  NITROGEN 


237 


According  to  Florence  MacCunn,  both  Sir  Walter  Scott  and  his 
mother  inherited  their  "homely  features  and  look  of  good-tempered 
shrewdness"  from  "old  Dr,  Rutherford,  whose  homely,  heavy,  sensible 
face  hangs  in  the  rooms  of  the  Edinburgh  College  of  Physicians"  (8). 

According  to  Lockhart,  Dr.  Daniel  Rutherford  "inherited  much  of 
the  general  accomplishments,  as  well  as  the  professional  reputation,  of  his 


Herman  Boerhaave,  1668-1738.  Dutch  physician, 
anatomist,  chemist,  and  botanist,  The  Edinburgh 
Medical  School  was  founded  by  pupils  o£  Boerhaave 
while  he  was  still  in  his  prime.  John  Rutherford, 
father  of  Daniel  Rutherford,  was  one  of  his  devoted 
disciples.  See  also  ref.  (42). 

father"  ( 9 ) .  He  was  keenly  interested  in  the  classics,  in  Snglish  literature, 
and  in  mathematics,  and  his  graduation  thesis,  like  that  of  his  celebrated 
professor,  Dr.  Joseph  Black,  clearly  revealed  the  existence  of  a  new  gas. 
Just  as  Black's  dissertation,  De  humore  acido  a  cibis  orto,  et  magnesia 
alba*  published  on  June  11,  1754,  together  with  his  "Experiments  upon 
Magnesia  Alba,  Quicklime,  and  Some  Other  Alcaline  Substances" 
( 1755 ) ,  had  clearly  characterized  the  gas  "fixed  air"  now  known  as  carbon 

*  The  acid  humor  arising  from  food,  and  magnesia  alba. 


238  DISCOVERY  OF  THE  ELEMENTS 

dioxide  (43),  Rutherford's  thesis,  Disseriatio  inauguralis  de  aere  fixo  dicto, 
aut  mephitico*  dated  September  12,  1772,  made  clear  the  existence  of 
nitrogen  ( phlogisticated  air)  as  distinct  from  carbon  dioxide. 

Although  Stephen  Hales  had  prepared  nitrogen  by  absorbing  the 
oxygen  from  a  confined  volume  of  atmospheric  air,  he  had  failed  to 
recognize  it  as  a  new  substance  (10).  Henry  Cavendish  was  evidently 
the  first  person  to  distinguish  nitrogen  from  other  kinds  of  suffocating 
incombustible  gases,  but  he  had  failed  to  publish  his  results.  In  a  paper 
marked  in  his  handwriting  "communicated  to  Dr.  Priestley/'  he  had 
written: 

I  am  not  ceitain  what  it  is  which  Dr.  P[riestley]  means  by  mephitic  air, 
though  from  some  circumstances  I  guess  that  what  he  speaks  of  ...  was  that 
to  which  Dr.  Black  has  given  the  name  of  fixed  air.  The  natural  meaning  of 
mephitic  air  is  any  air  which  suffocates  animals  (&  this  is  what  Dr.  Priestley 
seems  to  mean  by  the  woids) ,  but  in  all  probability  there  are  many  kinds  of  air 
which  possess  this  pioperty.  I  am  suie  there  are  2,  namely,  fixed  air,  &  common 
air  in  which  candles  have  burnt,  or  which  has  passed  thro'  the  fire.  Air  which 
has  passed  thro*  a  charcoal  fire  contains  >a  great  deal  of  fixed  air,  which  is  gen 
erated  from  the  charcoal,  but  it  consists  principally  of  common  air,  which  has 
suffered  a  change  in  its  nature  from  the  fire.  As  I  formerly  made  an  experiment 
on  this  subject,  which  seems  to  contain  some  new  circumstances,  I  will  here  set 
it  down. 

I  transferd  some  common  air  out  of  one  receiver  through  burning  charcoal 
into  a  2nd  receiver  by  means  of  a  bent  pipe,  the  middle  of  which  was  filled  with 
powdered  charcoal  &  heated  red  hot,  both  receivers  being  inverted  into  vessels 
of  water,  &  the  2nd  receiver  being  full  of  water,  so  that  no  air  could  get  into  it 
but  what  came  out  of  the  first  receiver  &  passed  through  the  charcoal.  The 
quant,  air  driven  out  of  the  first  receiver  was  180  oz.  measures,  that  driven  into 
the  2nd  receiver  was  190  oz.  measures.  In  order  to  see  whether  any  of  this  was 
fixed  air,  some  sope  leys  was  mixed  with  the  water  in  the  bason,  into  which  the 
mouth  of  this  2nd  receiver  was  immersed;  it  was  thereby  reduced  to  166  oz.,t 
so  that  24  oz.  meas.  were  absorbed  by  the  sope  leys,  all  of  which  we  may  con 
clude  to  be  fixed  air  produced  from  the  charcoal;  therefore  14  oz.  of  common 
air  were  absorbed  by  the  fumes  of  the  burning  charcoal,  agreeable  to  what  Dr. 
Hales  and  others  have  observed,  that  all  burning  bodies  absorb  air  .  .  .  (11). 

With  characteristic  thoroughness  Cavendish  had  passed  the  166 
ounces  of  residual  air  back  again  through  fresh  burning  charcoal  into 
another  receiver.  After  another  treatment  with  the  soap  lye  there 
remained  162  ounces  of  a  gas  which  he  described  as  follows: 

*  Inaugural  dissertation  on  the  air  called  fixed  or  mephitic. 

t  The  numher  168  given  in  the  British  Association  Reports  is  evidently  a  misprint. 


RUTHERFORD,   DISCOVERER  OF   NITROGEN 


239 


The  specific  gravity  of  this  air  was  found  to  differ  very  little  from  that  of 
common  air,  of  the  two  it  seemed  rather  lighter.  It  extinguished  flame,  & 
rendered  common  air  unfit  for  making  bodies  burn,  in  'the  same  manner  as  fixed 
air,  but  in  a  less  degree  .  .  . 


Sir  Walter  Scott,  1771-1832.  Scottish  novelist  and 
poet.  His  writings  contain  many  interesting  allusions 
to  his  uncle,  Dr.  Daniel  Rutherford.  Scott's  circle  of 
friends  included  Dr  William  Hyde  Wollaston,  Sir 
David  Brewster,  Dr,  John  Davy,  Sir  Humphry  Davy, 
and  Joseph  Black. 

In  a  paper  read  before  the  Royal  Society  in  March,  1772  (six  months 
before  Dr,  Rutherford's  thesis  was  published),  Priestley  mentioned  these 
experiments,  but  failed  to  record  Cavendish's  clear  interpretation  of  them. 

The  Honourable  Mr.  Cavendish  favoured  me  [said  he]  with  an  account  of 
some  experiments  of  his,  in  which  a  quantity  of  common  air  was  reduced  from 
180  to  162  ounce  measures,  by  passing  through  a  red-hot  iron  tube  filled  with 
the  dust  of  charcoal.  This  diminution  he  ascribed  to  such  a  destruction  of  com- 


240  DISCOVERY  OF  THE  ELEMENTS 

mon  air  as  Dr.  Hales  imagined  to  be  the  consequence  of  burning.  Mr.  Caven 
dish  also  observed,  that  there  had  been  a  generation  of  fixed  air  in  this  process, 
but  that  it  was  absorbed  by  sope  leys  (12). 

In  the  same  paper  Priestley  stated: 

Air  thus  diminished  by  the  fumes  of  burning  charcoal  not  only  extinguishes 
flame,  but  is  in  the  highest  degree  noxious  to  animals;  it  makes  no  effervescence 
with  iiitious  air,  and  is  incapable  of  being  diminished  any  further  by  the  fumes 
of  more  chaicoal,  by  a  mixture  of  iron  filings  and  brimstone,  or  by  any  other 
cause  of  the  diminution  of  air  that  I  am  acquainted  with,  This  obseivation, 
which  respects  all  other  kinds  of  diminished  air,  proves  that  Dr.  Hales  was  mis 
taken  in  his  notion  of  the  absorption  of  air  in  those  circumstances  m  which  he 
observed  it.  For  he  supposed  that  the  remainder  was,  m  all  cases,  of  the  same 
nature  with  that  which  had  been  absorbed,  and  that  the  operation  of  the  same 
cause  would  not  have  failed  to  produce  a  farther  diminution;  whereas  all  my 
observations  not  only  shew  that  an,  which  has  once  been  fully  diminished  by 
any  causes  whatever,  is  not  only  incapable  of  any  farther  diminution,  either  from 
the  same  or  from  any  other  cause,  but  that  it  has  likewise  acquired  new  proper 
ties,  most  remarkably  different  fiom  those  which  it  had  before,  and  that  they 
are,  in  a  great  measure,  the  same  in  all  the  cases  .  .  (12) . 

Priestley  also  observed  that  "lime-water  never  became  turbid  by  the 
calcination  of  metals  aver  it,"  and  that  "when  this  process  was  made  in 
quicksilver,  the  air  was  diminished  only  one-fifth;  and  upon  water  being 
admitted  to  it,  no  more  was  absorbed"  (12).  He  stated  that  this  "air  in 
which  candles,  or  brimstone,  had  burned  out  .  .  .  is  rather  lighter  than 
common  air"  (12).  Thus  Priestley  recognized,  even  at  this  early  date, 
some  of  the  most  important  properties  of  the  gas  now  known  as  nitrogen. 

Although  the  only  copy  of  Rutherford's  thesis  which  Sir  William 
Ramsay  was  able  to  find  is  in  the  British  Museum,  Dr,  Leonard  Dobbin 
found  a  copy  of  it  in  the  Edinburgh  University  Library  and  has  published 
Crum  BioWs  English  translation  of  it  in  the  Journal  of  Chemical  Educa 
tion  (40).  Although  Ramsay  stated  in  the  first  edition  of  "The  Gases  of 
the  Atmosphere"  that  this  dissertation  "precedes  Priestley's  and  Scheele's 
writings  by  a  year  or  two,"  he  conected  this  in  the  second  edition  to  read: 
"...  Priestley  had  nearly  anticipated  Rutherford;  and  indeed,  he  specu 
lated  on  the  nature  of  the  residual  gas,  left  after  combustion  and  absorp 
tion  of  the  fixed  air  produced"  (13).  Although  Rutherford  referred  in  his 
thesis  to  Priestley's  experiments  on  the  effect  of  vegetation  on  the  atmos 
phere,  he  was  evidently  unfamiliar  with  those  on  nitrogen  (14,15}. 

Dr.  Black  had  noticed  that  when  a  carbonaceous  substance  is  burned 
in  air  in  such  a  manner  that  the  fixed  air  can  be  absorbed  in  caustic  alkali, 
a  portion  of  the  air  remains.  He  had  therefore  assigned  to  his  student, 


RUTHERFORD,   DISCOVERER   OF    NITROGEN 


241 


Daniel  Rutherford,  the  investigation  of  this  residual  air  in  partial  fulfill 
ment  of  the  requirements  for  the  degree  of  doctor  of  medicine. 

The  dissertation  begins  with  an  appropriate  quotation  from  Lucretius 
and  a  review  of  the  researches  of  Black  and  of  Cavendish  on  fixed  air, 
Rutherford  then  described  his  own  experiments  in  which  he  had  found 
that  a  mouse,  left  in  a  confined  volume  of  atmospheric  air  until  it  died, 
had  consumed  Vie  of  the  air,  and  that  treatment  of  the  remaining  air 
with  alkali  had  caused  it  to  lose  one-eleventh  of  its  volume.  He  found 


From  Gentleman's  Magazine,  1799 

Stephen  Hales,  1677-1761,     British  clergyman,  biolo 
gist,   chemist,   and  inventor.      His  most  important  re 
searches   were   on  blood   pressure,    circulation  of   sap, 
respiration,  and  ventilation 


that  the  residual  air  extinguished  the  flame  of  a  candle  and  that  the  wick 
would  continue  to  glow  in  it  for  only  a  short  time.  He  also  discovered  that 
air  depleted  by  passage  over  ignited  charcoal  is  identical  with  air  vitiated 
by  respiration.  When  he  burned  a  metal,  phosphorus,  or  sulfur  in  the 
atmosphere,  however,  he  found  that  the  residual  gas  contained  no  mephitic 


242  DISCOVERY  OF  THE  ELEMENTS 

air  [carbon  dioxide],  but  that  it  had  undergone  "a  singular  change"  (14). 
After  burning  a  candle  or  suffocating  a  mouse  in  a  confined  volume  of 
air,  and  absorbing  the  resulting  faced  air,  or  carbon  dioxide,  in  caustic 
alkali,  Rutherford  concluded  from  careful  study  of  the  residual  gas  that 

.  healthy  and  pure  air  by  being  respired,  not  only  becomes  partly  mephitic 
[poisonous],  but  also  suffers  another  -change  in  its  nature.  For  after  all  mephitic 
air  [carbon  dioxide]  is  separated  and  removed  fiom  it  by  means  of  a  caustic 
lixivium,  that  which  remains  does  not  thence  become  more  healthful;  for  al 
though  it  makes  no  precipitate  of  lime  from  water,  yet  it  extinguishes  fee  and 
life  no  less  than  before  (16)  . 

Rutherford  also  believed  that  "pure  air  is  not  conveited  into  mephitic 
air  by  force  of  combustion,  but  that  this  air  rather  takes  its  rise  or  is 
thrown  out  from  the  body  thus  resolved"  (IS).  He  concluded,  in  other 
words,  "that  that  unwholesome  air  is  composed  of  atmospheric  air  in  union 
with,  and,  so  to  say,  saturated  with,  phlogiston"  (15).  After  pointing 
out  the  distinction  between  tins  new  "noxious  air"  [nitrogen]  and  "me 
phitic  air"  [carbon  dioxide],  the  air  evolved  by  the  action  of  acids  on 
metals,  and  the  air  from  decaying  flesh,  Rutherford  added  that  he  was 
unable  to  state  with  certainty  anything  regarding  the  composition  of 
mephitic  air  or  to  explain  its  inability  to  support  life.  He  believed,  how 
ever,  that  it  was  possibly  generated  from  the  food,  and  expelled  as  a  waste 
product  from  the  blood  by  means  of  the  lungs  (14). 

Certain  experiments  [said  the]  appear  to  show  .  ,  .  that  it  consists  of  at 
mospheric  air  in  union  with  phlogistic  material:  for  it  is  never  produced  except 
from  bodies  which  abound  in  inflammable  parts,  the  phlogiston  ever  appears  to 
be  taken  up  by  other  bodies,  and  is  hence  of  value  in  reducing  the  calces  of 
metals.  I  say  from  phlogistic  material,  because  as  already  mentioned,  pure 
phlogiston,  in  combination  with  common  air,  can  be  seen  to  yield  another  kind 
of  air  .  .  . 


Sir  William  Ramsay  believed  that  Rutherford  "may  well  be  credited 
with  the  discovery  of  nitrogen"  and  that  his  thesis  on  mephitic  air  "was 
an  advance,  though  not  a  great  one,  in  the  development  of  the  theory  of 
the  true  nature  of  air"  (15),  B.  B.  Woodward  believed,  however,  that 
"all  the  facts  and  views  recorded  by  Rutherford  are  to  be  found  in 
Priestley's  memoir  published  in  the  Philosophical  Transactions  for  1772 
(p.  230  et  passim),  and  read  six  months  before  the  publication  of  Ruther 
ford's  tract;  but  Priestley's  exposition  is  less  methodical  and  precise"  (14). 
Both  Rutherford  and  Priestley  believed  the  new  gas  to  be  atmospheric 
air  saturated  with  phlogiston,  and  neither  of  them  regarded  it  as  an 
element  (14). 


RUTHERFORD,  DISCOVERER  OF   NITROGEN  243 

In  his  "Lectures  on  the  Elements  of  Chemistry ,"  Dr.  Joseph  Black 
made  the  following  statement  about  the  discovery  of  nitrogen: 

Scarcely  inferior  to  vital  air  in  importance  is  the1  faul  air  of  Dr.  Scheele, 
which  I  mentioned  on  the  same  occasion,  as  that  noxious  portion  of  atmospheri 
cal  air  which  remains  when  the  vital  air  has  teen  absorbed  by  the  hepar  sul- 
phuris  [product  of  heating  potassium  carbonate  with  sulfur]  (17) .  I  must  here 
observe,  that  this  portion  of  our  atmosphere  was  first  observed  in  1772  by  my 
colleague  Dr.  Rutherford,  and  published  by  him  in  his  inaugural  dissertation 
He  had  then  discovered  that  we  were  mistaken  in  supposing  that  all  noxious 
air  was  -the  fixed  air  which  I  had  discovered.  He  says,  that  after  this  has  been 
removed  by  caustic  alkali  or  lime,  a  very  large  proportion  of  the  air  remains, 
which  extinguishes  life  and  flame  in  an  instant.  Soon  after  this  Dr.  Priestley 
met  with  this  noxious  air,  which  was  produced  in  a  variety  of  experiments,  in 
which  bodies  were  burned,  or  putrefied,  or  thickened  in  certain  cases,  or  metals 
calcined,  or  minerals  effloresced,  &c.&c.  In  all  these  cases,  he  thought  that  he 
had  reason  to  believe  that  phlogiston  had  quitted  the  substances  under  con 
sideration-had  combined  with  the  air,~and  had  thus  vitiated  it.  Now  saturated 
with  phlogiston,  the  air  could  take  no  more,  and  therefore  extinguished  flame. 
He  called  all  these  processes  phlogisticating  processes,  and  the  air  thus  tainted 
phlogisticated  air  (IS). 

According  to  Dr.  Black,  it  was  Scheele  who  proved  that  the  diminu 
tion  of  bulk  which  accompanied  the  vitiation  of  the  air  by  these 
combustion  processes 

.  was  owing  to  a  real  abstraction  of  all  the  vital  air  which  the  atmospheric 
air  contained.  For  when  any  of  these  "phlogisticating  processes"  of  Dr.  Priestley 
were  performed  in  vital  air,  it  was  totally  absorbed  (19) .  The  remainder  there 
fore,  when  the  experiment  was  made  in  common  air,  was  considered  by  him  as 
a  primitive  air,  unchanged  in  its  properties.  He  called  it  faul  air,  which  may 
mean  either  rotten  air,  because  it  is  produced  in  vast  abundance  by  putrefying 
bodies,  or  simply  foul  air,  L  e.9  tainted  occasionally,  when  the  phlogiston  is  more 
than  will  saturate  the  vital  air. 

Dr.  Black  also  mentioned  Berthollet's  preparation  of  nitrogen  by 
pouring  nitric  acid  on  fresh  muscle  fiber  and  Fourcroy's  discovery  of  this 
gas  in  the  swimming  bladders  of  carp,  bream,  and  other  fish  (20).  He 
said  that,  although  the  discoverers  of  the  element  had  called  it  by  various 
names-pWogisticated,  foul,  or  mephitic  air,  or  choke-damp  (Stickstoff)- 
the  name  nitrogen  had  been  suggested  by  "Mr.  Chaptal  and  other  chemists 
of  the  first  rank;'  after  Cavendish  had  prepared  niter  by  sparking  the  new 
gas  with  oxygen  in  presence  of  caustic  potash  (21).  The  French  name 
azote  was  suggested  by  Lavoisier  because  of  the  inability  of  the  gas  to 
support  life  (18,  22,  23,  24}.  Although  Lavoisier  (25)  had  mentioned 


244      DISCOVERY  OF  THE  ELEMENTS 

nitrogen  in  his  list  of  elements,  Sir  Humphry  Davy  doubted  its  elementary 
nature  as  late  as  1808-09  and  attempted  to  decompose  it  (26) 

After  his  graduation,  young  Dr.  Rutherford  studied  in  Paris,  Italy, 
and  London  for  three  years  before  returning  to  Edinburgh  to  practice 
medicine.  During  his  stay  in  Paris,  he  declined  an  invitation  to  a  party 
at  which  Prince  Charles  Edward  was  expected,  saying  that,  out  of  respect 
for  the  honor  of  a  fallen  house,  he  wished  to  avoid  the  spectacle  of  seeing 
the  prince  intoxicated  ( 1 ) . 

Since  Max  Speter  (27,  41 )  mentioned  that  John  Mayow  in  his  "Trac- 
tatus  Quinque"  anticipated  Lavoisier  (-28)  in  the  belief  that  all  acids 
contain  oxygen,  it  is  interesting  to  know  that  Dr.  Rutherford  also  made 
the  same  error.  A  note  by  John  Robison  in  his  edition  of  Black's  "Lectures 
on  the  Elements  of  Chemistry"  reads  as  follows: 

I  cannot  omit  mentioning  in  this  place,  that  my  colleague,  Dr.  Daniel 
Rutherford  read,  in  the  year  1775,  to  the  Philosophical  Society  of  Edinburgh,  a 
dissertation  on  nitre  and  nitrous  acid,  in  which  this  doctrine  is  more  than  hinted 
at  or  surmised.  By  a  series  of  judiciously  connived  experiments,  he  obtained  a 
great  quantity  of  vital  air  from  nitric  acid;  about  one-third  of  that  quantity  fi  om 
the  sulphuric  acid,  as  contained  in  alum,  and  a  small  quantity  (and  this  veiy 
variable  and  uncertain)  from  the  muriatic  acid.  The  manner  in  which  it  came 
off  from  the  compounds,  in  various  circumstances,  led  him  to  think  that  the 
different  quantities  obtained  did  not  arise  from  the  different  proportions  in  which 
it  was  contained  in  those  acids,  but  merely  in  the  different  forces  with  which  it 
was  retained.  He  therefore  concluded  that  vital  air  was  contained  in  all  acids, 
and  thought  it  likely  that  it  was  a  necessary  ingredient  of  an  acid;  and  seeing 
that  it  was  the  only  substance  found,  as  yet,  in  them  all,  he  thought  it  not  un 
likely  that  it  was  by  this  that  they  were  acid,  and  he  points  out  a  course  of  ex 
periments  which  seems  adapted  to  the  decision  of  this  question  I  was  appointed 
to  make  a  report  on  this  dissertation;  and  I  recollect  stating  as  an  objection  to 
Dr.  Rutherford's  opinion,  "that  it  would  lay  him  under  the  necessity  of  suppos 
ing  that  vitriolic  acid  was  a  compound  of  sulphur  and  vital  air,"  which  I  could 
not  but  think  an  absurdity.  So  near  were  we  at  that  time  to  the  knowledge  of 
the  nature  of  the  acids  (29). 

Mayow's  "Tractatus  Quinque"  was  published  in  1674,  Dr.  Ruther 
ford's  communication  was  read  in  1775,  and  Lavoisier's  statement  that 
oxygen  is  an  essential  constituent  of  all  acids  is  contained  in  a  paper  read 
on  November  23,  1779. 

In  1786  Rutherford  was  appointed  successor  to  John  Hope,  the  pro 
fessor  of  botany  at  the  University  of  Edinburgh,  and  in  the  same  year  he 
was  married  to  Harriet  Mitchelson  of  Middleton  (1),  With  pardonable 
family  pride,  Sir  Walter  Scott  once  said  that  Dr.  Rutherford  "ought  to 
have  had  the  chemistry  class,  as  he  was  one  of  the  best  chemists  in  Europe; 


RUTHERFORD,   DISCOVERER  OF   NITROGEN  245 


Fiom  Kay's  Portraits 

John  Hope,  1725-1786.  Predecessoi  of  Daniel  Ruther 
ford  as  professor  of  botany  and  materia  medica  at  the 
University  of  Edinburgh.  Dr  Hope  had  the  plants  in 
the  Botanical  Garden  arranged  according  to  the  Linnaean 
system,  In  the  above  portrait  he  is  shown  instructing 
one  of  the  workmen.  His  son,  Thomas  Charles  Hope 
(1766-1844),  was  Rutherford's  contemporary  as  pro 
fessor  of  chemistry  at  Edinburgh 


but  superior  interest  assigned  it  to  another,  who,  though  a  neat  experimen 
talist,  is  not  to  be  compared  to  poor  Daniel  for  originality  of  genius.  .  ." 
(30).  Bower's  "History  of  the  University  of  Edinburgh"  states  that  the 
discovery  of  nitrogen  "entitles  Rutherford  to  rank  very  high  among  the 
chemical  philosophers  of  modern  times"  and  that  "the  reputation  of  his 
discovery  being  speedily  spread  through  Europe,  his  character  as  a 
chemist  of  the  first  eminence  was  firmly  established,  and  much  was 


246  DISCOVERY   OF  THE  ELEMENTS 

augured  from  a  young  man  in  his  twenty-second  year  having  distinguished 
himself  so  remarkably"  (30). 

Sir  R.  Christison,  one  of  Dr.  Rutherford's  botany  students,  said,  on 

the  other  hand, 

Tradition  had  it  m  my  student  years  that  he  was  disappointed  at  not  being 
made  assistant  and  successor  to  Black  m  1795,  when  that  office  was  given  to 
Dr.  Charles  Hope,  and  he  again,  son  of  the  botanical  predecessor  of  Rutherford, 
was  said  to  have  preferred  to  step  into  his  own  father's  University  shoes  rather 
than  into  those  of  Dr.  Black.  However  that  may  have  been,  Hope  highly  dis 
tinguished  himself  in  his  Chemical  Chair;  while  Rutherford,  in  that  of  Botany, 
which  he  filled  for  thirty-four  years,  always  seemed  to  lecture  with  a  grudge,  and 
never  contributed  a  single  investigation  to  the  progress  of  the  science  which  he 
taught.  .  .  His  lectuies,  however,  were  extremely  clear,  and  full  of  condensed 
information,  his  style  was  beautiful,  and  his  pronunciation  pure  and  scarcely 
Scotch  (31). 

Because  of  hereditary  gout,  Dr.  Rutherford  was  unable  to  take  his 
botany  students  on  field  trips,  and  Sir  R.  Christison  thought  that  that 
important  duty  ought  to  have  been  entrusted  to  the  head  gardener  (31). 

I.  B.  Balfour  also  thought  it  strange  that  Dr.  Rutherford  should  have 
been  chosen  to  teach  botany,  and  stated  in  the  "Makers  of  British  Botany" 
that  "Rutherford  was  a  chemist,  and  I  have  not  discovered  in  any  refer 
ences  to  him  expressions  that  he  was  at  this  period  of  his  life  interested 
in  plants  otheiwise  than  as  objects  for  his  experiments  in  relation  to  the 
chemistry  of  the  atmosphere"  (32).  Nevertheless,  the  botanical  garden 
developed  under  Rutherford's  administration  into  one  of  the  best  in  the 
world,  and  the  plants  of  Scotland  were  carefully  recorded  by  the  head 
gardeners  (32). 

Dr.  Rutherford  was  a  fellow  of  the  Philosophical  (later  the  Royal) 
society  of  Edinburgh,  and  contributed  to  its  Transactions  a  description 
of  a  thermometer  for  reading  maximum  and  minimum  temperatures  (33, 
34).  The  portion  of  the  instrument  designed  for  reading  minimum 
temperatures  is  a  horizontal  tube  filled  with  alcohol  in  which  is  immersed 
a  small  glass  rod  with  a  knob  at  each  end.  As  long  as  the  temperature 
keeps  falling,  the  concave  surface  tension  film  of  the  alcohol  drags  this 
little  rod  back  with  it,  but  when  the  temperature  rises,  the  expanding 
alcohol  moves  past  the  rod,  leaving  it  stationary.  The  portion  of  the 
thermometer  used  for  reading  maximum  temperatures  consists  of  a  hori 
zontal  tube  containing  a  thread  of  mercury  which  pushes  a  small  bar  of 
iron  ahead  of  it  as  long  as  'the  temperature  keeps  rising  (34) .  Dr.  Ruther 
ford  also  made  experiments  to  improve  the  air  pump  (33). 

He  published  an  octavo  volume  called  "Characteres  Generum  Plan- 
tarum,"  and  collaborated  with  James  Hamilton  and  James  Gregory  in 


RUTHERFORD,  DISCOVERER  OF   NITROGEN  247 


From  Kay's  Portraits 

Cartoon  Showing  a  Controversy  in  1817  over  the  Founding  of  a  Chair  of 
Comparative  Anatomy.  The  Candidate,  Dr.  Barclay,  is  shown  astride  the 
elephant's  skeleton.  His  opponent,  Dr.  Thomas  Charles  Hope  (center  fore 
ground),  has  his  anchor  firmly  grounded  in  "the  strontian."  This  is  an  allusion 
to  the  research  in  which  he  distinguished  between  baryta  and  strontia.  The 
scene  is  laid  at  the  entrance  to  the  old  College  of  Edinburgh. 


writing  "A  Guide  for  Gentlemen  Studying  Medicine  at  the  University  of 
Edinburgh"  (14).  He  was  a  member  of  the  Linnsean  Society  and  of  the 
Aesculapian,  Harveian,  and  Gymnastic  Clubs  (14). 

Dr.  and  Mrs.  Rutherford  had  two  sons  and  three  daughters,  but  in 
1805  the  elder  son,  John,  a  boy  of  seventeen,  was  lost  in  the  shipwreck 
of  an  East  Indiaman  commanded  by  John  Wordsworth,  a  brother  of  the 
famous  poet.  After  his  words  of  sympathy  to  William  Wordsworth,  Scott 
wrote,  "...  The  same  dreadful  catastrophe  deprived  me  of  a  near 
relation,  a  delightful  and  promising  youth,  the  hope  and  pride  of  his 
parents.  He  had  just  obtained  a  cadetship,  and  parted  from  us  all  in  the 
ardor  of  youthful  hope  and  expectation,  leaving  his  father  ( a  brother  of 
my  mother)  almost  heartbroken  at  his  departure.  .  ."  (.35).  Fourteen 
years  later  Scott  said,  when  writing  to  his  son  at  the  time  of  Dr.  Ruther 
ford's  death,  "Since  you  knew  him,  his  health  was  broken  and  his  spirits 
dejected,  which  may  be  traced  to  the  loss  of  his  eldest  son  ,  .  ."  (30). 

Scott's  correspondence  with  his  aunt,  Miss  Christian  Rutherford, 
shows  that  he  found  in  his  uncle's  family  ".  .  .  more  than  one  kind  and 


248  DISCOVERY  OF  THE  ELEMENTS 

strenuous  encourager  of  his  early  literary  tastes."  Nevertheless,  his  youth 
ful  habit  of  reading  at  breakfast  often  brought  forth  good-natured  protest 
from  the  doctor  (9), 

In  December,  1819,  Scott  suffered  the  tragic  loss  of  three  of  his 
nearest  relatives  within  scarcely  more  than  a  week  (30,  36).  On  the 
twelfth,  his  mother,  who  had  been  in  excellent  health  and  spirits  in  spite 


.a . a- 


«_a — o y  js    "    «P,   «    w    7Q    IP    1° 


tit    lie,   &    *t>    »h    A    ri  Va    ti    A    a 


/» 


Rutherford's   Maximum   and  Minimum    Thermometer,      a, 
Index   of  minimum  thermometer;   m,   Index   of  maximum 

thermometer. 


of  her  advanced  age  of  eighty-seven  years,  was  suddenly  stricken  with 
such  a  severe  attack  of  paralysis  that  Dr.  Daniel  Rutherford  felt  certain 
that  she  could  not  live  more  than  a  few  days. 

But  [said  Scott  in  a  letter  to  his  brother  in  Canada],  "tins  heavy  calamity 
was  only  the  commencement  of  our  family  losses.  Dr  [Daniel]  Rutherford,  who 
had  seemed  perfectly  well  and  had  visited  my  mother  upon  Tuesday  the  four 
teenth,  was  suddenly  affected  with  gout  in  his  stomach,  or  some  disease  equally 
rapid,  on  Wednesday  the  fifteenth,  and  without  -a  moment's  warning  or  com 
plaint,  fell  down  a  dead  man,  almost  without  a  single  groan.  You  are  aware  of 
his  fondness  for  animals;  he  was  just  stroking  his  cat  after  eating  his  breakfast, 
as  usual,  when,  without  more  warning  than  a  half-uttered  exclamation,  ihe  sunk 
on  the  ground,  and  died  in  the  arms  of  his  daughter  Anne.  Though  the  Doctor 
had  no  formed  complaint,  yet  I  have  thought  him  looking  poorly  for  some 
months;  and  though  there  was  no  failure  whatever  in  intellect,  or  anything 
which  approached  it,  yet  his  memory  was  not  so  good,  and  I  thought  he  paused 
during  the  last  time  he  attended  me,  and  had  difficulty  in  recollecting  the  pre 
cise  terms  of  'his  recipe.  Certainly  there  was  a  great  decay  of  outward  strength. 

We  were  very  anxious  about  the  effect  this  fatal  news  was  likely  to  produce 
on  the  mind  and  decayed  health  of  our  aunt,  Miss  C.  Rutherford,  and  resolved, 
as  her  health  tad  been  gradually  falling  off  ever  since  she  returned  from  Abbots- 
ford,  that  she  should  never  learn  anything  of  it  until  it  was  impossible  to  con 
ceal  it  longer.  But  God  had  so  ordained  it  that  she  was  never  to  know  the  loss 
she  had  sustained,  and  which  she  would  have  felt  so  deeply.  On  Friday  the 
17th  December,  the  second  day  after  her  brother's  death,  she  expired,  without 
a  groan  and  without  suffering,  about  six  in  the  morning.  ...  It  is  a  most 
uncommon  and  afflicting  circumstance,  that  a  brother  and  two  sisters  should  be 


RUTHERFORD,  DISCOVERER  OF   NITROGEN  249 

taken  ill  the  same  day— that  two  of  them  should  die  without  any  rational  possi 
bility  o£  the  survi vance  of  the  third— and  that  no  one  of  the  three  could  be 
affected  'by  learning  the  loss  of  the  other.  The  Doctor  was  buned  on  Monday 
20th,  and  Miss  Rutherford  this  day  (Wednesday  22nd),  in  the  burial-place 
adjoining  to  and  surrounding  one  of  the  new  Episcopal  chapels  [St.  John's 
Chapel],  where  Robert  Rutherford  [son  to  the  professor  of  botany]  had  pur 
chased  burial-ground  of  some  extent  .  ,  .  and  in  this  new  place  I  intend  to  lay 
our  poor  mother  when  the  scene  shall  close  ,  .  .  (37) 

Scott  once  paid  the  following  tribute  to  his  uncle:  "Dr.  Rutherford 
was  a  very  ingenious  as  well  as  an  excellent  man,  more  of  a  gentleman 
than  those  of  his  profession  too  often  are,  for  he  could  not  take  the  back 
stairs  mode  of  rising  in  it,  otherwise  he  might  have  been  much  more 
wealthy  .  .  ."  (30).  This  kindly  Scottish  physician  is  remembered  today 
for  his  maximum  and  minimum  thermometer  and  for  the  brilliant  research 
in  which  he  clearly  distinguished  between  carbon  dioxide  and  nitrogen 
(38,  39). 

LITERATURE  CITED 

(1 )  ROGERS,  C  ,  "Genealogical  Memoirs  of  the  Family  of  Sir  Walter  Scott,  Bart,  of 

Abbotsford,"  Roy.  Historical  Soc.,  London,  1877,  pp   Iv-lviu. 

(2)  LOCKHART,  J.  G,  "Memoirs  of  the  Life  of  Sir  Walter  Scott/*  Vol.  1,  Adam  & 

Charles  Black,  Edinburgh,  1862,  p.  14. 

(3)  LOCKHART,  J.  G.,  ref.  (2),  Vol.  1,  pp.  19-21, 

(4)  "Catalogue  of  tie  Scott  Centenary  Exhibition,"  Edinburgh  University  Press, 

Edinburgh,  1872,  p.  149. 

(5)  LOCKHART,  J.  G  ,  ref.  (2),  Vol.  1,  p.  ±73. 

( 6 )  ROGERS,  C.,  ref.  ( I ) ,  p.  In. 

( 7 )  GRANT,  SIR  ALEXANDER,  "The  Story  of  the  University  of  Edinburgh  during  Its 

Fust  Three  Hundred  Years,"  Vol.  1,  Longmans,  Green  &  Co  ,  London,  1884, 
pp.  308-15 

(8)  MACCUNN,  F.,  "Sir  Walter  Scott's  Friends,"  Wm.  Blackwood  &  Sons,  Edin 

burgh  and  London,  1910,  p.  12. 

(9)  LOCKHART,  J.  G  ,  ref.  (2),  Vol.  1,  p.  188. 

(10)  CLARK-KENNEDY,   A    E.,   "Stephen   Hales,   D.D.,   FRS.,"   University   Press, 

Cambridge,  1929,  pp.  101-10 

( 11 )  HARCOURT,  V.,  "Presidential  address/'  Brit    Assoc.  Reports,  9,  3-68    ( Aug. 

1839 ) .    A  reprint  of  Cavendish's  paper  on  nitrogen  is  included. 

(12)  PRIESTLEY,  J.,  "Observations  on  different  kinds  of  air/'  Phil.  Trans,  62,  147- 

256  (1772)     Read  Mar.  5,  12,  19,  26  (1772). 

(13)  RAMSAY,  SIR  W,  "The  Gases  of  the  Atmosphere,"  1st  ed ,  Macmillan  &  Co., 

London,  1896,  p.  62,  ibid.,  2nd  ed.,  1915.,  p.  63 

(14)  LEE,  Sm  SIDNEY,  "Dictionary  of  National  Biography/'  Vol.  50,  The  Macmillan 

Co  ,  New  York  City,  1897,  pp.  5-6.    Article  on  Daniel  Rutherford  by  B   B 
Woodward. 

( 15)  RAMSAY,  Sm  W.,  ref.  (IS),  2nd  ed.,  pp  62-8 

(16)  GRANT,  Sm  ALEXANDER,  ref   (7),  Vol.  2,  pp.  382-4, 

(17)  SCHEELE,  C.  W,  "Nachgelassene  Briefe  und  Aufzeichmingen,"  Nordenskiold 

edition,  P.  A.  Norstedt  &  Soner,  Stockholm,  1892,  p.  80     Letter  of  Scheele 
to  J   G  Gahn,  Nov.,  1775. 


250  DISCOVERY  OF  THE  ELEMENTS 

(IS)     BLACK,  JOSEPH,  "Lectures  on  the  Elements  of  Chemistry/'  Vol  2,  Wm.  Creech, 
Edinburgh,  1803,  pp.  105-8. 

(19)  DOBBIN,  L  >  "The  Collected  Papers  of  Carl  Wilhelm  Scheele/'  G,  Bell  &  Sons, 

London,  1931,  pp.  116-7. 

(20)  FOURCROY,  A.-F.,  "Recherches  pour  servir  a  Hiistoire  du  gaz  azote  ou  de  la 

mofette,  comme  principe  des  matieres  animates,"  Ann  chim.  phys ,  [1],  1, 
40-7  (1795);  "Observations  sur  le  gaz  azote  contenu  dans^la  vessie  natatoire 
de  la  carpe;  deux  nouveaux  precedes  pour  obtenir  ce  gaz,"  ibid*,  [1],  1,  47- 
51  (1795), 

(21)  Alembic  Club  Reprint  No.  3,  "Experiments  on  Air.     Papers  published  in  the 

Philosophical  Transactions  by  the  Honourable  Henry  Cavendish,  F.RS./' 
Wm  F.  Clay,  Edinburgh,  1893,  pp  39-52;  PI  CAVENDISH,  Phil  Trans ,  75, 
372-84  ( 1785).  Read  June  2,  1785. 

(22)  BLACK,  JOSEPH,  ref.  (18),  Vol.  1,  pp.  395-6. 

(23)  BLACK,  JOSEPH,  ref.  (18),  Vol.  1,  p.  Iv. 

(24)  "Oeuvres  de  Lavoisier,"  Vol.   1,  Imprimerie   Impenale,   Paris,   1864,  p.   63, 

''Nitrogen  and  phosphorus.  Classic  of  science,"  Sci  News  Letter,  22,  102-4 
(Aug.  13,  1932), 

(25)  "Oeuvres  de  Lavoisier,"  ref.  (24),  Vol.  1,  pp.  135-7. 

(26)  DAVY,  H.,  "The  Bakerian  lecture.     An  account  of  some  new  analytical  re 

searches  on  the  nature  of  certain  bodies,"  Phil  Trans.,  99,  55-6,  103-4 
( 1809 )  Read  Dec.  15,  1808. 

(27)  SPETER,  MAX,  "John  Mayow  und  das  Schicksal  seiner  Lehren,"  Chem.-Ztg., 

34,  946-7,  953-4,  962-4  (Sept.  1910),  Alembic  Club  Reprint  No.  17,  Uni 
versity  of  Chicago  Press,  Chicago,  111.,  1908,  pp  31-2.  Translation  of  May- 
ow's  "Tractatus  Quinque  Medico-Physici  " 

(28)  "Oeuvres  de  Lavoisier,"  ref.  (24),  Vol.  1,  p.  57;  ibid.,  Vol    2,  pp    248-60. 

Paper  read  Nov.  23,  1779.    Presented  Sept  5,  1777. 

(29)  BLACK,  J.,  ref.  (18),  Vol.  2,  p  213  (note  6)  and  p.  732 

(30)  LOCKHART,  J.  G.,  ref.  (3),  Vol.  6,  pp.  157-9.     (Letter  of  Sir  W.  S.  to  his  son, 

Cornet  Walter  Scott),  BOWER,  "History  of  the  University  of  Edinburgh/' 
Vol.  3  1830,  pp.  260-1.  Quoted  by  Lockhart. 

(31 )  GRANT,  SIR  ALEXANDER,  ref.  (7),  Vol,  2,  pp,  382^4. 

(32)  OLIVER,  F.  W.?  "Makers  of  British  Botany/'  Cambridge  University  Press,  Cam 

bridge,  1913,  pp.  290-1  Chapter  by  I.  B.  Balfour  on  "A  sketch  of  the  pro 
fessors  of  botany  in  Edinburgh  from  1670  until  1887." 

(33)  POGGENDORFF,  J.  C.,  "Biographisch-Literansclies  Handworterbuch  der  exakten 

Wissenschaften/'  Vol.  2,  Verlag  Chemie,  Leipzig  and  Berlin,  1863-1937, 
p.  726.  Article  on  Daniel  Rutherford 

(34)  EDSER,  E.,  "Heat  for  Advanced  Students,"  Macmillan  &  Co.,  London,  1911, 

pp  18-9;  R.  T.  GLAZEBROOK,  "Heat,"  Cambridge  University  Press,  Cam 
bridge,  1914,  p  25,  T  PRESTON,  "Theory  of  Heat/'  2nd  ed ,  Macmillan  & 
Co.,  London,  1904,  p,  113. 

(35)  DOUGLAS,  DAVID,  "Familiar  Letters  of  Sir  Walter  Scott/'  Vol.  1,  Houghton 

Mifflin  Co  ,  Boston,  1894,  p.  27. 

(36)  LOCKHART,  J.  G.,  ref.  (2),  Vol.  6,  pp.  160-1;  D.  DOUGLAS,  ref.  (35),  Vol,  2, 

pp.  66  and  69-70  (Letters  of  Sir  Walter  Scott  to  Wm.  Laidlaw,  to  J.  B. 
Morritt,  and  to  Joanna  Baillie. ) 

(37)  LOCKHART,  J.  G.,  ref.  (2),  Vol.  6,  pp.  164-8.     (Letter  of  Sir  Walter  to  his 

brother,  Thomas  Scott.) 

(38)  WEEKS,  M.  E.,  "The  discovery  of  the  elements.    IV.    Three  important  gases," 

J.  Chem  Educ.,  9,  219-21  (Feb.  1932). 

(39)  "DAN    RUTHERFORD   uber   die  mephitische  Luft,"  Vol    12,    Crell's   Neueste 

Entdeckungen  in  der  Cherrne,  Weygandsche  Buchhandlung,  Leipzig,  1784. 
pp.  187-96. 


RUTHERFORD,  DISCOVERER   OF    NITROGEN  251 

(40)  DOBBIN,  L.,  "Daniel  Rutherford's  inaugural  dissertation.     Crum  Brown's  trans 

lation/'  ].  Chem.  Educ.,  12,  370-5  (Aug.,  1935). 

( 41 )  SPETER,  MAX,  "Lavoisier  und  seine  Vorlauf er/'  F.  Enke,  Stuttgart,  1910,  pp 

56-72,  96-108.    Chapter  on  John  Mayow 

(42)  ATKINSON,  E.  R.,  ^Samuel  Johnson*s  Life  of  Boerhaave,"  /.  Chem.  Educ ,  19, 

103-8  (Mar,  1942) 

(43)  NEAVE,  E.  W.  J.?  "Joseph  Black's  lectures  on  the  elements  of  chemistry/'  Isis, 

25,  372-90  (Sept,  1936). 


J.  L.  H.  Borjeson's  Statue  of 
Carl  Wilhelm  Scheele.  Scheele 
discovered  tungstic  and 
molybdic  acids,  and  was  the 
"first  to  distinguish  between 
graphite  and  molybdenite. 


From  Nordenskiold's  "Carl  Wilhelm  Scheele. 
Wachgelassene   Briefe  und 


"Les  laboratories  sont  les  temples  de  I'avenir,  de  la 
richesse  et  du  bien-dtre;  cest  la  que  rhumanite 
grandit,  se  fortifie  et  dement  meilleure."  (I)* 

"It  is  to  a  general  diffusion  of  a  knowledge  of  chem 
istry,  next  to  the  Virtue  of  our  countrymen,  that  we 
are  to  look  for  the  firm  establishment  of  our  Inde 
pendence"  (71). 

*  "Laboratories  are  the  temples  of  the  future,  of  wealth,  and  of  welfare;  in  them 
humanity  grows  greater,  stronger,  and  better." 


9 

Chromium,  molybdenum,  tungsten,  uranium 


The  publications  and  correspondence  of  Bergman  and  Scheele 
contain  interesting  allusions  to  the  de  Elhuyar  brothers,  to  Hjelm, 
and  to  the  early  history  of  the  metals  tungsten  and  molybdenum 
which  they  discovered.  The  presence  of  a  new  metal  in  pitch 
blende  was  recognized  by  Klaproth  in  1 789,  but  it  remained  for 
Peligot  half  a  century  later  to  isolate  uranium.  Chromium,  now 
the  most  familiar  element  of  the  group,  was  the  last  to  be  dis 
covered  when  the  immortal  French  chemist  Vauquelin  finally 
isolated  it  in  1798  from  a  Siberian  mineral.  For  further  informa 
tion  about  tungsten  see  pp.  284-301. 


D 


uring  the  last  two  decades  of  the  eighteenth  century,  investi 
gations  were  made  which  foreshadowed  the  discovery  of  chromium, 
molybdenum,  tungsten,  uranium,  tellurium,  chlorine,  titanium,  and  beryl 
lium;  but  some  of  these  elements  were  not  actually  isolated  until  much 
later.  For  the  sake  of  simplicity,  only  the  closely  related  elements,  tungs 
ten,  molybdenum,  uranium,  and  chromium,  will  be  considered  in  this 
chapter. 

TUNGSTEN  (WOLFRAM) 

Tungsten  and  tungstic  acid  were  first  recognized  in  the  minerals 
wolframite  and  scheelite.  As  early  as  1761,  J.  G,  Lehmann  analyzed  the 
former,  without  recognizing,  however,  that  it  contained  two  metals  which 
were  then  unknown,  tungsten  and  manganese.  When  he  fused  it  witii 
sodium  nitrate  and  dissolved  the  melt  in  water,  he  obtained  a  green 
solution  which  became  red  (sodium  manganate  and  permanganate), 
Addition  of  a  mineral  acid  caused  the  precipitation  of  a  soft,  spongy, 
white  "earth  (tungstic  acid)"  which,  after  long  standing  in  contact  with 
the  solution,  became  yellow.  He  concluded,  however,  that  the  wolframite 
from  Zinnwald  must  be  "a  mineral  consisting  mainly  of  a  glassy  earth, 
much  iron,  and  a  trace  of  zinc"  and  that  it  is  related  to  a  mineral  used 
by  glassmakers,  "magnesia  vitriariorum"  or  pyrolusite  (58). 

253 


254  DISCOVERY  OF  THE  ELEMENTS 


Lampadius'  Laboratory  at  Freiberg,  1800.  Many  of 
the  most  eminent  mmeralogical  chemists  in  Europe 
were  educated  at  the  Freiberg  School  of  Mines.  The 
de  Elhuyar  brothers,,  who  discovered  tungsten,  and 
A.  M.  del  Rio,  who  discovered  vanadium  ("erythro- 
nmm"),  received  part  of  their  training  there,  and  F 
Reich  and  H.  T.  Richter,  the  discoverers  of  indium,  and 
Clemens  Winkler,  the  discoverer  of  germanium,  were 
members  of  the  teaching  staff. 


In  1779  Peter  Woulfe  examined  this  mineral  and  concluded  that  it 
must  contain  something  new.  "The  Spar  of  the  Germans,"  said  he,  "is 
commonly  called  white  tin  ore.  .  .  .  This  is  supposed  by  several  to  be 
rich  in  tin;  but  the  Saxon  mineralogists  assert  that  it  contains  none.  The 
only  experiment  I  made  with  it  was  to  digest  it  in  a  powdered  state  with 
acids,  by  which  means  i«t  acquires  a  rich  yellow  colour,  like  turbith  mineral 
[basic  mercuric  sulfate];  the  acid  of  salt  answers  best  for  this  experiment. 
This  is  the  only  substance  I  know  of  which  has  this  property"  (65). 

There  is  found  in  Sweden  a  white  mineral  which  used  to  be  called 
tungsten,  or  heavy  stone,  and  which  is  now  known  as  scheelite  (20).  In 
1781  Scheele  gave  the  following  description  of  it:  "The  constituents  of 
this  variety  of  stone  seem  probably  to  be  still  unknown  to  chemists.  Cron- 
stedt  enumerates  it  amongst  the  ferruginous  varieties  of  stone,  under  the 
name  of  Ferrum  calciforme,  terra  quadam  incognita  intime  mioctum.  That 
which  I  used  for  my  experiments  is  pearl-coloured  and  taken  from  the 
iron  mine  of  Bitsberg"  (56).  He  decomposed  the  mineral  with  aqua  f ortis 


CHROMIUM,  MOLYBDENUM,  TUNGSTEN,  URANIUM  255 

(nitric  acid)  and  found  that  it  contained  lime  and  a  white  acidic  powder 
similar  to  molybdic  acid  but  diftering  from  it  in  the  following  respects: 

"(1)  The  acid  of  molybdaena  is  volatile  and  melts  in  the  fire,  which 
does  not  occur  with  acid  of  tungsten.  (2)  The  first-named  acid  has  a 
stronger  affinity  for  phlogiston,  which  is  seen  from  its  union  with  sulphur 
and  the  change  it  undergoes  on  calcination  with  oil.  (3)  Calx  molyb- 
daenata  does  not  become  yellow  with  acid  of  nitre  and  is  dissolved  by  it 
quite  easily.  With  tungsten  the  contrary  occurs.  (4)  Terra  ponderosa 
molybdaenata  is  soluble  in  water,  but  not  the  same  variety  of  earth  united 
with  our  acid;  and  (5)  acid  of  molybdaena  has  a  weaker  attraction  for 
lime  than  our  acid"  (56). 

Thinking,  because  of  its  high  specific  gravity,  that  scheelite  might 
contain  the  alkaline  earth  baryta,  Torbern  Bergman  analyzed  it,  but  found 
instead  an  acidic  oxide  (tungstic  acid).  In  1781  he  concluded  -that  both 
tungstic  and  molybdic  acids  must  be  related  to  white  arsenic  and  that 
therefore  it  ought  to  be  possible  to  prepare  metals  from  them.  Since 
Bergman  himself  could  not  find  tune  to  test  this  hypothesis,  he  expressed 
the  hope  that  someone  else  would  make  the  necessary  experiments  (57). 

In  the  meantime  two  Spanish  chemists,  the  de  Elhuyar*  brothers, 
discovered  in  wolfram,  a  dark  brown  mineral  (wolframite)  then  supposed 
to  be  an  ore  of  tin  and  iron,  an  acid  (wolf ramie)  which  they  found  to  be 
identical  with  tungstic  acid  (2,  21,  25,  37,  38). 

Don  Fausto  de  Elhuyar  was  born  in  1755  at  Logrono,  Spain.  With 
his  elder  brother,  Don  Juan  Jose,  he  went  to  Freiberg  to  study  chemistry 
and  mineralogy  at  the  School  of  Mines,  and  Don  Juan  Jose  later  went  to 
Upsala  to  work  for  half  a  year  in  Bergman's  famous  laboratory  (21,  41}. 
The  Swedish  professor  mentioned  him  in  his  diary.  "Mr.  de  Luyarte, 
from  Spain,"  said  he,  "came  with  Mr  de  Virly  to  Upsala  on  the  same 
errand  [to  study],  where  they  not  only  privately  went  through  an  entire 
course  in  higher  chemistry,  but  also,  with  others,  went  to  private  lectures 
in  assaying,  each  passing  excellent  tests.  They  remamed  until  the  end  of 
the  term"  (27,39). 

In  a  letter  to  Bergman  dated  July  5,  1782,  Scheele  mentioned  a  visit 
which  these  chemistry  students  had  recently  paid  him:  ".  .  .  The  foreign 
gentlemen,"  he  said,  "stayed  with  me  two  days,  I  found  real  pleasure  in 
talking  with  them  about  chemical  matters;  moreover  they  were  not  inex 
perienced  in  that  field"  ( 3 ) . 

In  1783  the  brothers  collaborated  in  a  research  on  tungsten  and 
wolfram,  and  found  that  both  these  ores  contained  the  tungstic  acid  that 
Scheele  had  reported.  The  first  metallic  tungsten  was  prepared  not  from 

*  The  name  was  also  spelled  Luyarte,  de  Luyaxt,  and  d'Elhuyart.     In  Spanish  books 
it  is  spelled  de  Elhuijar.    The  brothers  themselves  did  not  agree  as  to  the  spelling 


256  DISCOVERY  OF  THE  ELEMENTS 

scheelite  but  from  wolframite  (spuma  lupi)  from  Zinnwald.  "We  know 
no  Spanish  name  for  this  mineral,"  wrote  the  de  Elhuyar  brothers  in  1783, 
"nor  do  we  know  that  it  has  been  found  in  our  country"  (58).  The 
possibility  of  obtaining  a  new  metal  by  reducing  tungstic  acid  had  already 
been  suggested  by  Bergman  and  Scheele.  The  apparatus  used  by  the 
de  Elhuyar  brothers  was  very  simple.  An  intimate  mixture  of  tungstic 
acid  and  powdered  charcoal  was  heated  strongly  in  a  luted  crucible  (22). 
After  cooling  the  crucible,  they  removed  from  it  a  dark  brown,  metallic 
button,  which  crumbled  easily  in  their  fingers,  and  when  they  examined 


Fausto  de  Elhuyar.  President  of  the 
Mining  Tribunal  and  Director  General  of 
Mines  of  New  Spam  For  more  than 
thirty  years  he  directed  the  College  of 
Mines  of  Mexico. 


Courtesy  Dr   Moles  and 
Mr.  de  Gdluez-Canero 


the  powder  with  a  lens,  they  saw  metallic  globules  of  tungsten,  some  of 
which  were  as  large  as  the  head  of  a  pin  (2,  26).  On  April  2,  1784. 
Scheele  wrote  to  Bergman,  "I  am  glad  that  Mr.  Luyarte  has  obtained  a 
tungsten  regulus.  I  hope  he  has  sent  you  specimens  of  it"  (4}. 

The  de  Elhuyar  brothers  afterward  went  to  America  and  in  1788 
Fausto  became  Director  of  Mines  of  Mexico.  Don  Juan  Jose  died  in 
Bogota,  Colombia,  but  at  the  outbreak  of  the  Revolution  Don  Fausto 
returned  to  Spain.  His  reason  for  leaving  Mexico  may  be  inferred  from 
the  note  found  at  the  end  of  one  of  Andres  del  Rio's  papers: 

The  preceding  analysis  only  too  plainly  shows  the  wretched  state  of  our 
laboratory  in  Mexico,  after  having  been  for  thirty  years  under  the  direction  of 
so  distinguished  a  chemist  as  M.  Elhuyar,  the  discoverer  of  wolfram  and 
cerium[!].*  It  is  true  that  under  the  old  government,  this  savant  found  himself 
obliged  to  become  a  man  of  business,  undoubtedly  much  against  his  inclination; 
for  it  is  impossible  that  he  who  has  once  imbibed  a  taste  for  science  can  ever 
abandon  it  (5). 

*  See  also  pp.  551  and  554. 


CHROMIUM,  MOLYBDENUM,  TUNGSTEN,  UBANIUM  257 

Torbern  Bergman  wrote  in  1784:  "In  connection  with  tungsten  I 
would  like  to  mention  that  the  bright-colored  species  from  Riddarhyttan, 
which  Herr  Cronstedt  cites,  does  not  belong  to  the  tungstens.  At  any 
rate,  ah1  those  which  I  myself  have  collected  on  the  spot  or  received  from 
others  show  an  entirely  different  behavior:  Herr  Director  de  Elhuyar 
indeed  carried  out  at  Upsala  an  analysis  in  the  wet  way  which  yielded 
per  hundredweight  besides  24  iron  and  22  silica  nothing  but  lime"  (94). 
Bergman  was  referring  here  to  the  "Director  of  all  of  the  smelting  works 
in  New  Granada,"  hence  not  to  Don  Fausto  but  to  Don  Juan  Jose  de 
Elhuyar. 

After  returning  to  Spain  Fausto  served  on  the  General  Council  of 
Public  Credit,  was  made  Director  General  of  Mines,  drew  up  the  famous 
mining  law  of  1825,  and  planned  the  School  of  Mines  of  Madrid.  After 
a  long,  eventful,  and  useful  life,  he  died  in  Madrid  on  January  6,  1833 
(6). 

In  1785  Rudolf  Erich  Raspe,  author  of  'The  Adventures  of  Baron 
Miinchausen,"  showed  that  the  metal  obtained  from  scheelite  is  identical 
with  that  from  wolframite  and  that  it  hardens  steel  (59).  In  an  investiga 
tion  of  two  refractory  specimens  of  scheelite,  he  succeeded  in  reducing 
them  to  a  "regulus  which  contains  only  a  little  iron  and  is  unusually  hard, 
strong,  and  refractory.  It  cuts  glass  like  good  hardened  steel  and  is  there 
fore  well  suited  for  the  manufacture  of  all  kinds  of  hard  tools,  for  the 
improvement  of  several  iron-  and  steel  manufactures,  even  perhaps  for 
the  pouring  of  anchors  in  a  single  operation."  He  also  prepared  a  fine 
yellow  pigment  from  the  mineral. 

When  he  compared  a  regulus  from  wolframite  with  one  from 
scheehte,  he  found  that  the  former  contained  more  iron  and  that  "it  has 
almost  the  same  color  as  the  scheehte  regulus  and  is,  if  I  be  not  mistaken, 
one  and  the  same  thing.  Only  yesterday  I  began  the  experiments  with 
wolframite,  which  I  regard  as  a  kind  of  crystallized  scheelite  and  which, 
according  to  a  report  in  the  newspapers,  Don  Luyarte  [de  Elhuyar]  and 
another  Spaniard  have  recently  announced  as  containing  a  new  metal" 
( 59 ) .  J.  Hawkins  said  that  Raspe  obtained  his  wolframite  from  "Poldice" 
[Poldise],  Cornwall  and  his  scheelite  from  Entral  (60).  Wolframite  is 
now  known  to  be  a  ferrous  manganous  tungstate  of  the  composition  (Fe, 
MnjWCX;  scheelite  is  calcium  tungstate,  CaWO^. 

Rudolf  Erich  Raspe  was  born  in  1737  in  Hanover  and  educated  in 
the  natural  sciences  and  philology  at  Gottingen  and  Leipzig.  Benjamin 
Franklin  met  both  Raspe  and  Baron  von  Munchausen  on  his  visit  in  Han 
over  ( 61 ) .  Raspe  was  brilliant  and  versatile,  but  extravagant  and  dis 
honest.  After  he  had  pawned  some  valuable  medals  which  he  had  stolen 
from  the  museum  at  Cassel,  the  police  described  him  as  a  red-haired  man, 


258  DISCOVERY  OF  THE  ELEMENTS 

attired  alternately  in  a  gold-embroidered  red  suit,  and  suits  of  black,  blue, 
and  gray.  After  his  arrest  at  Clausthal,  he  escaped  in  the  night  and 
embarked  for  England,  where  for  die  rest  of  his  life  he  earned  his  living 
by  tutoring  and  translating.  He  was  also  employed  for  a  time  in  the  mines 
of  Cornwall  and  Ireland.  He  died  at  Mucross,  Ireland,  in  1794  (62,  95). 

When  M.  H.  Klaproth  analyzed  some  supposed  specimens  of  scheelite 
and  wolframite  from  Poldise,  Cornwall,  in  1786,  he  found  that  the  former 
had  not  been  correctly  identified  but  that  the  wolframite  was  genuine. 
He  was  unable  to  reduce  tungstic  acid  to  a  metal,  even  in  a  smelting 
furnace  or  in  the  kilns  of  the  Royal  Porcelain  Works  (72). 

As  late  as  1800,  F.  C.  Gren  wrote:  "It  is  still  questionable  whether 
the  oxyd  of  wolfram  is  reducible  to  a  reguline  metal.  No  chemist  has  yet 
succeeded  in  obtaining  a  pure  regulus  of  it,  at  least  of  some  magnitude. 
Whenever  the  experiment  was  attempted,  the  result,  upon  examination 
with  the  glass,  was  always  found  to  be  a  mere  congeries  of  small  metallic 
globules"  (63). 

Nicholsons  Journal  for  the  same  year  contained  a  brief  account  of 
Guyton  de  Morveau's  attempt  to  fuse  tungsten:  "Guyton,  in  a  fire  urged 
by  the  blast  of  three  pipes  to  185  degrees  of  the  pyrometer,  obtained  a 
well  rounded  piece  of  35  grammes.  But  it  broke  in  the  vice,  and  exhibited 
a  central  portion,  which  was  only  agglutinated,  and  soon  acquired  a  purple 
colour  by  exposure  to  the  air  .  .  and  he  concludes  from  the  infusibility 
and  brittleness  of  this  metal  that  it  affords  little  promise  of  utility  in  the 
arts,  except  in  metallic  alloys,  or  by  virtue  of  the  property  which  its  oxide 
possesses,  of  affording  fixed  colours,  or  giving  fixity  to  the  colours  of 
vegetables"  (64}.  The  tungsten  lamp  filaments,  tungsten  contact  points, 
high-speed  steel,  and  cutting  tools  tipped  with  hard  diamond-like  tungsten 
carbide  (Widia)  so  indispensable  to  modern  life  have  all  resulted  never 
theless  from  the  great  discovery  made  so  long  ago  by  the  de  Elhuyar 
brothers  in  Spain.  Tungsten,  in  the  opinion  of  W.  P.  Sykes,  "has  a  value 
to  civilization  extremely  large  in  proportion  to  the  small  amount  in  pounds 
used  as  lamp  filaments.  This,  however,  is  sufficient  to  save  the  people  of 
the  United  States  alone  some  three  billions  of  dollars  each  year  as  com 
pared  with  the  expenditures  which  would  be  required  to  produce  the 
same  level  of  illumination  with  carbon  filament  lamps"  (93), 

MOLYBDENUM 

Native  molybdenum  disulfide  is  a  soft,  black  mineral  that  looks  much 
like  graphite.  In  fact,  until  the  latter  part  of  the  eighteenth  century,  both 
were  sold  under  the  same  name:  Molybddn,  or  molybdenum.  German 
writers  used  to  call  molybdenite  "Wasserbley,"  a  name  suggestive  of  lead, 


CHROMIUM,  MOLYBDENUM,  TUNGSTEN,  TJRANIUM  259 

Although  Johann  Heinnch  Pott  knew  that  It  is  not  a  lead  mineral,  he  con 
fused  it  with  graphite,  "Reissbley/'  and  believed  that  it  contained  lime, 
iron,  and  sulfuric  acid  (50). 

In  1754  Bengt  (Andersson)  Qvist,  a  friend  of  A.  F.  Cronstedt  and 
Sven  Rinman5  investigated  a  mineral  which  he  described  as  follows:  "At 
one  locality  of  the  Bispberg  there  is  found  a  light,  roughly  pointed,  loose, 


Courtesy  Fansteel  Products  Co ,  Inc 
Vacuum  Tube  Showing  the  Use  of  Tantalum  and  Molybdenum 


glistening  molybdenite  [Wasserblei]  consisting  of  flexible  lamellae  which 
are  not  firmly  coherent  and  which  for  the  most  part  succeed  one  another 
in  the  form  of  regular  pyramids.  ...  In  the  muffle  it  gave  off  dense 
black  fumes  and  a  suffocating  sulfurous  odor;  at  the  same  time  appeared 
small  yellow  "flowers"  like  snowflakes,  which  crystallized  in  masses  of 
rather  elastic  filaments  or  lamellae"  (51). 

Qvist  observed  that  the  calx  was  yellow  while  hot  but  glistening 
white  when  cold,  He  obtained  positive  tests  for  iron  and  copper,  and 
found  that  "on  digestion,  it  gave  no  sweetness  to  distilled  vinegar"  (an 
indication  that  molybdenite  is  not  a  lead  mineral) .  In  one  specimen  from 
England  he  detected  tin.  He  concluded  that  <cit  is  evident  from  several 
experiments  that  the  molybdenite  itself  contains  something  specifically 
metallic  in  addition  to  those  just  mentioned"  (51). 


260  DISCOVERY  OF  THE  ELEMENTS 

On  December  19,  1777,  Scheele  wrote  to  J.  G.  Gahn:  "You  doubtless 
have  there  in  your  mineral  collection  some  foliated  molybdaena  like  the 
enclosed  sample.  I  received  some  in  the  summer  from  Assessor  Hoffgaard; 
I  find  something  peculiar  in  it.  Please  be  so  good  as  to  send  me  a  little 
of  it  by  mail.  On  some  better  occasion  I  shall  describe  my  experiments" 
(52). 

Scheele  kept  this  promise,  and  on  May  15th  of  the  following  year 
wrote  Gahn  as  follows:  "I  now  have  the  pleasure  of  giving  you  a  short 
report  of  my  experiments  with  molybdaena.  Professor  Bergman,  Assessor 
Rinman,  and  B.  Hermelin  [Samuel  Gustav  Hermelin]  all  sent  me  some  of 
it"  (52). 

In  1778  Scheele  published  his  analysis  of  the  so-called  "lead  ore" 
(molybdenite),  then  known  as  molybdaena.  "I  do  not  mean  the  ordinary 
lead  ore,"  said  he,  "that  is  met  with  in  the  apothecaries'  shops,  for  this  is 
very  different  from  that  concerning  which  I  now  wish  to  communicate  my 
experiments  to  the  Royal  Academy.  I  mean  here  that  which  in  Cronstedt's 
"Mineralogy"  is  called  molybdaena  membranacea  nitens  and  with  which 
Qvist  and  others  probably  made  their  experiments.  The  kinds  I  had 
occasion  to  submit  to  tests  were  got  in  different  places,  but  they  were  all 
found  to  be  of  the  same  nature  and  composed  of  the  same  constituents" 
(53). 

Because  of  its  softness,  Scheele  had  to  devise  an  ingenious  method  of 
pulverizing  the  mineral.  "Now  since  it  does  not  permit  of  being  ground 
to  fine  powder  by  itself,  on  account  of  its  flexible  lamellae,  some  fragments 
of  vitriolated  tartar  [potassium  sulfate]  were  also  placed  in  the  glass 
mortar  occasionally,  when  it  was  at  last  transformed  to  a  fine  powder" 
(53).  Scheele  then  washed  the  powder  by  decantation  with  hot  water 
to  remove  the  potassium  sulfate.  By  adding  nitric  acid  to  the  mineral 
several  times  and  evaporating  to  dryness,  he  succeeded  in  decomposing  it 
so  completely  that  only  a  white  powder  remained,  which  he  named  terra 
molybdaenae. 

Bengt  Qvist  had  already  shown  that  the  mineral  is  volatile  in  the 
open  fire  and  that  it  contains  sulfur,  and  Scheele  found  that  "earth  of 
molybdaena  is  of  an  acid  nature."  He  examined  it  "by  the  method  of 
reduction  with  black  flux  and  charcoal  and  with  glass  of  borax  and  char 
coal,  but  it  was  in  vain;  I  did  not  perceive  anything  in  the  least  metallic" 
(53).  Scheele  showed  that  graphite  and  the  molybdenum  mineral  are  two 
entirely  different  substances.  Although  nitric  acid  has  no  effect  on 
graphite,  it  reacts  with  the  mineral  "molybdenum,"  or  molybdenite,  to 
give  sulfuric  acid  and  a  peculiar  white  solid,  which  he  named  molybdic 
acid  (2,  23).  Bergman  suggested  to  Scheele  that  molybdic  acid  must  be 
the  o^ide  of  a  new  metal?  and  since  the  latter  chemist  did  not  have  a 


CHROMIUM,  MOLYBDENUM,  TUNGSTEN,  URANIUM  261 

furnace  suitable  for  the  purpose,  he  asked  his  friend  Hjelm  to  attempt  the 
reduction  of  the  ore  (7). 

Peter  Jacob  Hjelm  was  of  about  the  same  age  as  Scheele,  for  he  was 
born  on  October  2,  1746,  at  Sunnerbo  Harad.  He  probably  met  the  latter 
in  Upsala,  for  their  correspondence  began  shortly  before  Scheele  went 
to  Koping  (7).  At  Scheele's  suggestion  Hjelm  tried  to  reduce  molybdic 
acid  with  carbon,  and  in  order  to  get  very  intimate  contact  between  the 
two  reagents,  he  stirred  the  pulverized  acid  with  linseed  oil  to  form  a 


Torbern  Olof  Bergman,  1735-1784.    Swedish  chemist,  pharmacist,  and  phys 
icist.     He  was  among  the  first  to  investigate  the  compounds  of  manganese, 
cobalt,  nickel,  tungsten,  and  molybdenum.     He  was  an  "immediate  fore 
runner  of  Haiiy"  in  the  history  of  theoretical  crystallography  (68). 

paste.  When  he  heated  the  mixture  strongly  in  a  closed  crucible,  the 
oil  became  carbonized,  and  the  carbon  reduced  the  molybdic  acid  to  the 
metal,  which  became  known  as  molybdenum  (2,  24). 

On  September  28,  1781  Scheele  wrote  to  Torbern  Bergman,  "I  am 
pleased  that  Herr  Hjelm  has  reduced  molybdic  acid"  ( 8 ) .  On  November 
16,  1781,  Scheele  wrote  to  Hjelm, 

...  I  gladly  excuse  your  delay  in  writing,  for  I  know  you  are  now  very 
busy.  I  rejoice  that  we  now  have  another  new  half-metal,  molybdaenum.  I 
think  I  can  already  see  the  French  seeking  to  deny  the  existence  of  this  new 
half-metal,  since  they  are  not  the  discoverers  of  it.  What  about  Meyer?  Here 
we  have  another  new  half-^netal,  and  it  is  fine  that  Meyer  and  Bergman  have 
discovered  it  at  -almost  the  same  time.  Who  then  deserves  the  honor  of  being 
called  its  discoverer?  If  you  want  to  read  Meyer's  article  on  it  in  German,  I 
shall  mail  it  to  you.  But  molybdaena  it  certainly  is  not,  although  it  seems  to 
resemble  it  in  many  respects.  Enclosed  herewith  is  my  entire  supply  of  acido 


262  DISCOVERY  OF  THE  ELEMENTS 

molybdaenae,  which,  to  be  sure,  is  made  with  saltpeter,  but  not  with  saltpeter 
in  the  fire.  The  acidum  enclosed  in  paper  is  the  same  acid  that  I  fused  in  a 
crucible.  If  you  prepare  a  regulus  from  it,  I  beg  you,  because  of  its  rarity,  to 
send  me  some  of  it,  even  if  it  is  only  a  grain.  I  have  no  molybdaenum  (8) . 

The  other  "half -metal"  referred  to  in  the  preceding  letter  was  "hydro- 
siderum,"  a  false  element  which  Apothecary  Johann  Karl  Friedrich  Meyer 
of  Stettin,  Scheele,  and  M.  H.  Klaproth  later  proved  to  be  a  phosphate 
of  iron  (73,  74,  41).  In  another  of  his  letters  to  Hjelm  Scheele  said,  "As 
far  as  I  can  judge  of  your  work,  it  does  you  all  credit"  (9).  Although  this 
correspondence  shows  that  Hjelm  must  have  isolated  molybdenum  as 
early  as  the  fall  of  1781,  his  first  paper  on  it  was  not  published  until 
much  later. 

Justus  Christian  Heinrich  Heyer,  in  the  account  of  his  own  researches 
on  molybdenite,  stated  in  1787  that  he  had  been  unable  to  find  from  the 
literature  how  Hjelm  had  prepared  the  metal  (75).  Heyer  repeated 
Scheele's  synthesis  of  molybdenite  by  heating  a  mixture  of  molybdic  acid 
and  flowers  of  sulfur  in  a  glass  retort  (75).  In  1790,  after  both  Scheele 
and  Bergman  had  died,  Hjelm  wrote: 

"At  the  request  of  the  late  Scheele  and  Bergman,  I  tried  to  prepare  a 
metal  from  yellow  molybdic  acid,  using  the  same  acid  which  the  former 
himself  sent  me.  I  first  fused  ox  blood  several  times  with  the  vegetable 
alkali;  then,  when  I  wanted  to  reduce  the  acid,  I  added  to  it  an  equal 
amount  of  microcosmic  salt,  and  a  little  tartar  or  black  flux  from  which  I 
had  often  smoked  off  some  grease.  I  placed  the  entire  mixture,  some 
times  also  covered  with  common  salt,  in  a  luted  crucible,  and  exposed  it 
for  several  hours  to  the  heat  of  a  good  wind  furnace.  If  one  wishes  to 
reduce  a  new  portion  of  acid  again,  one  uses  the  glass  produced  in  the 
foregoing  operation,  as  it  might  then  be  less  inclined  to  attack  the  earth 
of  molybdenum  itself  and  to  dissolve  it. 

"The  small  regulus  I  obtained  from  the  meager  supply  of  earth 
brought  forth  the  description  of  it  to  be  found  in  Herr  Bergman's  paper 
on'  the  blowpipe.  The  traces  of  sulfur  and  iron  present  in  the  reguluses  I 
attribute  to  the  molybdic  earth  which  I  received,  for  my  fluxes  were 
perfectly  pure;  the  former  were  therefore  only  a  kind  of  crude  metal  in 
which,  however,  the  metallic  nature  is  fundamental.  Several  writers, 
including  Herr  [Bertrand]  Pelletier,  Sage,  Ilsemann,  and  Heyer,  assume 
this:  yet  they  have  not  engaged  in  the  actual  reduction"  (42) . 

Hjelm  prepared  purified  molybdic  acid  and  obtained  a  pure  regulus, 
which  he  examined  with  the  microscope.  In  an  unsuccessful  attempt  to 
fuse  the  molybdenum,  he  raised  the  temperature  of  the  wind-furnace  with 
"fire-air"  '(oxygen)  obtained  by  adding  two  pounds  of  crude  pyrolusite 
to  the  fire  (24). 


CHROMIUM,  MOLYBDENUM,  TUNGSTEN,  URANIUM 


263 


He  published  papers  on  the  composition  of  coal,  wood,  charcoal, 
steel,  pyrolusite,  molybdenite,  and  spring  waters,  on  the  arts  of  purifying 
lead,  hardening  copper,  and  burning  bricks,  on  the  working  of  saltpeter 
and  indigo,  on  resuscitation  of  patients  with  suspended  animation,  and 
on  the  porphyry  industry  at  Elfdal,  East  Dalarne  (54). 

In  1782  Hjelm  was  made  Assay  Master  of  the  Royal  Mint  at  Stock 
holm,  and  twelve  years  later  he  became  Director  of  the  Chemistry  Labora 
tory  at  the  Bureau  of  Mines.  He  died  in  that  city  on  October  7,  1813  ( 7) . 

Edward  Daniel  Clarke,  who  visited  him  in  1799,  described  him  as 
"a  most  intelligent  man  and  very  able  chemist,  of  the  name  of  Hjelm, 


Martin  Heinrich  Klaproth,  1743-1817. 

German  chemist  and  pharmacist.  The 
most  distinguished  German  mineralogi- 
cal  and  analytical  chemist  of  his  time. 
His  careful  analyses  led  to  the  discov 
ery  of  uranium  and  zirconium  and  veri 
fied  the  discovery  of  tellurium  and 
titanium.  He  also  made  pioneer  re 
searches  on  ceria  (97). 


who  permitted  us  to  see  the  collection  of  minerals  belonging  to  the 
Crown.  .  .  .  Mr.  Hjelm  was  employed,  at  the  time  of  our  arrival,  in 
making  what  he  called  Spa  Water,  that  is  to  say,  water  impregnated 
with  carbonic  acid  gas,  by  the  usual  process  of  agitating  the  fluid  in  a 
receiver  containing  the  gas  collected  from  the  effervescence  of  lime 
stone  when  exposed  to  the  action  of  an  acid.  Mr.  Hjelm  used  the  sul 
phuric  acid  and  powdered  marble.  He  showed  to  us  a  very  great  chemical 
curiosity;  namely,  a  mass  of  chromium  in  the  metallic  state,  nearly  as 
large  as  the  top  of  a  man's  thumb.  We  could  perceive,  however,  that  the 
Swedish  chemists,  celebrated  as  they  justly  are,  carry  on  their  works  in 
the  large  way:  the  furnaces  used  by  Mr.  Hjelm,  in  the  Royal  Laboratory, 
were  of  the  size  of  those  in  our  common  blacksmiths'  shops;  and  the 
rest  of  his  apparatus  was  on  a  similar  scale"  (55). 


264  DISCOVERY  OF  THE  ELEMENTS 

Professor  Hjelm  was  one  of  Scheele's  best  friends,  and  their  corre 
spondence  is  still  treasured  by  the  Stockholm  Academy  of  Sciences. 
Hjelm's  diary  is  now  in  possession  of  the  Royal  Library  at  Stockholm  (7). 
When  Scheele  wrote  to  Hjelm,  "Es  1st  fa  nur  die  Wahrheit,  welche  wir 
wissen  wollen,  und  welch  ein  herrliches  Gefuhl  1st  es  nicht,  sie  erforscht 
zu  haben9*  (10),  he  knew  that  he  was  expressing  the  latter's  feelings 
as  well  as  his  own. 

In  1785  B.  Pelletier  proved  that  the  ore  mineralogists  used  to  call 
"molybdenum"  is  a  sulfide  of  that  metal  (28).  The  molybdic  acid 
obtained  by  Scheele  does  not  exist  as  such  in  the  mineral,  but  was 
produced  when  he  oxidized  the  molybdenum  sulfide  with  nitric  acid. 

In  1790  Baron  Ignaz  von  Born  announced  in  Crell's  Annalen  that 
Anton  Rupprecht,  professor  at  the  Mining  Academy  in  Selmeczbanya, 
Hungary,  had  prepared  molybdenum  (67). 

Although  molybdenite  was  for  several  years  the  only  known  source 
of  molybdenum,  the  Abbe  F.  X.  Wulfen  in  1785  described  a  lead  mineral 
from  Carinthia  which  had  previously  been  regarded  as  lead  tungstate, 
and  when  M.  H.  Klaproth  analyzed  a  specimen  of  it  from  Bleyberg  in 
1792-94,  he  found  it  to  be  lead  rnolybdate  ( 76 ) .  Two  years  later,  Charles 
Hatchett  examined  a  larger  specimen  of  it  and  confirmed  Klaproth's  con 
clusion.  This  mineral  is  now  known  as  wulfenite. 

Molybdenum  is  a  much  softer,  more  ductile  metal  than  tungsten, 
and  is  indispensable  for  the  filaments,  grids,  and  screens  required  in  radio 
broadcasting.  Hence  this  great  modern  industry  rests  upon  the  researches 
that  gave  so  much  intellectual  pleasure  to  Hjelm  and  Scheele. 

URANIUM 

When  R.  T.  Gunther  of  Oxford  University  was  excavating  the  Im 
perial  Roman  Villa  on  Cape  Posilipo  on  the  Bay  of  Naples  he  discovered 
a  richly  colored  glass  mosaic  mural  which  for  archaeological  and  his 
torical  reasons  he  believed  to  date  from  approximately  79  A.D.  A  speci 
men  of  the  pale  green  glass  from  it  which  was  analyzed  at  Oxford  Uni 
versity  in  1912  was  found  to  contain  more  than  one  per  cent  of  an  oxide 
of  uranium.  After  a  careful  study  of  the  evidence,  Earle  R.  Caley  con 
cluded  that  the  addition  of  a  uranium  mineral  to  the  glass  was  probably 
intentional  and  that  the  date  79  A.D.  may  be  "taken  as  fixing  the  approxi 
mate  time  of  the  first  use  of  uranium  glass  and  the  approximate  time  of 
the  first  use  of  any  kind  of  a  material  containing  uranium"  (69). 

The  early  history  of  uranium  is  closely  associated  with  the  name  of 

*  "It  is  only  the  truth,  that  we  want  to  know,  and  isn't  it  a  glorious  feeling  to  have 
discovered  it?" 


CHROMIUM,  MOLYBDENUM,  TUNGSTEN,  URANIUM 


265 


Martin  Heinrich  Kfoproth,  a  German  chemist  who  was  born  in  Werni- 
gerode  in  the  Harz  on  December  1,  1743.  When  he  was  eight  years  old, 
the  family  became  impoverished  by  a  serious  fire.  Since  there  was 
little  money  left  for  the  education  of  the  three  Klaproth  boys,  little  Martin 
Heinrich  earned  his  tuition  by  singing  in  the  church  choir.  After  re 
ceiving  a  little  instruction  in  Latin  at  Wernigerode,  he  was  apprenticed 
at  the  age  of  sixteen  years  to  an  apothecary.  After  five  years  of  appren 
ticeship,  he  worked  for  four  years  in  public  laboratories  at  Quedlinburg 


Valentin  Rose  the  Younger,  1762-1807.* 

German  chemist  and  apothecary  who  was 
educated  by  Klaproth,  collaborated  with 
him  in  his  researches,  and  verified  all  his 
analyses  before  publication.  Rose  dem 
onstrated  the  presence  of  chromium  in 
a  species  of  serpentine.  He  was  the 
father  of  Heinrich  Rose,  the  chemist,  and 
Gustav  Rose,  the  mineralogist.  His  fa 
ther,  Valentin  Rose  the  Elder,  was  the 
discoverer  of  the  low-melting  alloy,  Rose's 
metal. 


From  Ferchl's  "Von  Libau  bis  Liebig" 


and  at  Hanover,  and  at  Easter  time  in  1768  he  became  an  assistant  in 
Wendland's  laboratory  in  Berlin  "at  the  sign  of  the  Golden  Angel  in  the 
street  of  the  Moors"  (11,  40). 

In  1770  he  became  an  assistant  to  the  famous  chemist,  Valentin  Rose, 
who,  however,  died  only  a  few  months  later.  Although  Klaproth  was 
only  twenty-seven  years  old  when  this  emergency  arose,  he  met  all  the 
responsibilities  of  his  new  position.  He  not  only  carried  on  Rose's  duties 
for  nine  years,  but  acted  as  a  father  to  his  two  fatherless  sons,  providing 
carefully  for  their  education.  The  younger  boy  unfortunately  died  in 
childhood,  but  the  older  one,  Valentin  Rose  the  Younger,  shared  Klaproth's 
love  for  nature,  and  collaborated  with  him  in  many  researches.  It  was 
Rose's  task  to  repeat  and  verify  all  Klaproth's  experiments  before  the 

*  Reproduced  by  courtesy  of  Mr.  Arthur  Nemayer,  Buchdruckerei  und  Verlag, 
Mittenwald,  Bavaria. 


266  DISCOVERY  OF  THE  ELEMENTS 


results  were  published  (11).  Klaproth  afterward  purchased  the  Flem- 
ming  laboratory  on  Spandau  Street.  His  wife  Christiane  Sophie  Lech- 
mann  was  a  relative  of  A.  S.  Marggraf.  They  had  six  children,  and  the 
only  son,  Heinrich  Julius,  became  a  famous  Orientalist  (97). 

Martin  Heinrich  Klaproth  made  many  brilliant  contributions  to 
analytical  and  mineralogical  chemistry  (33),  and  was  a  pioneer  in  the 
chemical  investigation  of  antiquities  such  as  Greek,  Roman,  and  Chinese 
coins,  ancient  glasses,  and  prehistoric  metallic  objects  (70).  His  papers 
are  assembled  in  his  "Beitrage  zur  chemischen  Kenntniss  der  Mineral- 
korper,"  a  six-volume  work.  Although  he  never  discovered  an  element 
in  the  sense  of  isolating  it  for  the  first  time,  his  analytical  work  fore 
shadowed  the  discovery  of  uranium  and  zirconium  and  verified  the 
discovery  of  tellurium  and  titanium. 

Pitchblende.  Early  chemists  and  mineralogists  believed  that  pitch 
blende  was  an  ore  of  zinc  and  iron.  When  M.  H.  Klaproth  first  recog 
nized  in  1789  that  it  contained  an  unknown  metal,  he  sketched  its 
history  as  follows:  "Of  late,  seventeen  metallic  substances  have  been 
acknowledged  as  distinct  metals,  each  of  a  nature  peculiar  to  itself.  The 
design  of  this  essay  is  to  add  one  to  that  number,  the  chemical  properties 
of  which  will  be  explained  in  the  sequel.  The  particular  fossil  by  the 
decomposition  of  which  I  have  discovered  this  new  metallic  substance 
is  the  black,  or  pitch-blende  (pseudo-galena  of  many)  as  it  has  been 
hitherto  called.  In  the  meantime  I  shall  continue  to  use  that  appellation, 
till,  in  the  progress  of  this  essay,  the  necessity  of  giving  it  a  new  name 
will  be  conspicuous.  This  fossil  is  found  at  Joachimsthal  in  Bohemia, 
and  at  Johann  Georgenstadt,  in  the  metalliferous  mountains  of  Saxony 

(77). 

"Only  a  few  writers,"  continued  Klaproth,  "appear  to  have  been 
formerly  acquainted  with  this  mineral.  .  .  .  Werner,  to  whom  its  fracture, 
hardness,  and  gravity  sufficiently  indicated  that  it  could  not  be  a  blende, 
has  transferred  it  from  the  class  of  zinc-ores  to  that  of  the  ores  of  iron, 
calling  it  Eisen-pecherz;  though  only  ad  interim,  until  its  proper  place 
should  be  ascertained  by  chemical  analysis.  A  subsequent  conjecture 
of  his,  that  this  fossil  might,  perhaps,  contain  the  metallic  radical  of 
tungsten,  or  Wolfram,  was  thought  to  be  supported  by  actual  experi 
ments  made  at  Schemnitz.  But  this  pretended  fact  is  contradicted  by 
the  result  of  the  following  examination"  (77). 

Klaproth  mentioned  two  kinds  of  pitchblende,  the  first  of  which 
was  a  brownish  black,  opaque,  brittle,  massive,  resplendent  kind  with 
a  conchoidal  fracture,  found  in  the  mines  or  galleries  at  Joachimsthal, 
Saxon  Edelleutstolln,  and  Hohe  Tanne. 

"The  second  variety,"  said  he,  "to  which  belongs  the  greatest  part 
of  pitch-blende  that  occurs  at  Johann-Georgenstadt,  is  greyish  black, 


CHROMIUM,  MOLYBDENUM,  TUNGSTEN,  URANIUM  267 

and  exhibits  various  degradations,  from  the  glittering  to  the  dull  or  dim. 
At  that  place  it  is  obtained  in  the  mine  Georg  Wagsfort,  in  larger  or 
smaller  masses,  between  strata  of  schistose  mica  [Glimmerschiefer]; 
which  is  nearly  in  a  state  of  decay.  ...  It  has  also  been  met  with  there 
in  the  mine  Neujahrsmaassen,  between  alternate  strata  of  the  fibrous 
iron-stone"  (77). 

When  Klaproth  dissolved  some  pitchblende  in  nitric  acid  and 
neutralized  the  acid  with  potash,  he  obtained  a  yellow  precipitate  which 
dissolved  in  excess  potash.  Klaproth  concluded  correctly  that  the  mineral 
must  contain  a  new  element,  which  he  named  in  honor  of  the  new  planet, 
Uranus,  which  Herschel  had  recently  discovered  ( 12 ) .  He  then  attempted 
to  obtain  metallic  uranium  just  as  Hjelm  had  prepared  metallic  molyb 
denum.  By  strongly  heating  an  oil  paste  of  the  yellow  oxide  in  a  charcoal 
crucible,  he  obtained  a  black  powder  with  a  metallic  luster,  and  thought 
he  had  succeeded  in  isolating  metallic  uranium  (29).  For  over  fifty 
years  the  elementary  nature  of  his  product  was  accepted  by  chemists, 
but  in  1841  Peligot  showed  that  this  supposed  uranium  metal  was  really 
an  oxide. 

When  the  University  of  Berlin  was  founded,  Klaproth  was  sixty- 
seven  years  old,  yet  he  was  appointed  as  the  first  professor  of  chemistry, 
and  served  in  that  capacity  until  his  death  on  January  1,  1817  (13). 
Thomas  Thomson  mentioned  as  his  most  characteristic  personal  traits: 
pure  love  of  science,  intellectual  integrity,  unselfishness,  modesty,  friendli 
ness,  kindness,  a  sense  of  humor,  religious  feeling,  freedom  from  super 
stition,  neatness,  and  precision  (14). 

In  1823  J.  A.  Arfwedson  reduced  the  green  oxide  of  uranium  (then 
believed  to  be  the  lowest  oxide)  with  hydrogen,  and  obtained  a  brown 
powder  which  he  took  to  be  the  metal,  but  which  is  now  known  to  be 
uranous  oxide,  UO2  (15,  30).  In  1841  Peligot,  on  analyzing  anhydrous 
uranous  chloride,  UC14,  found  that  100  parts  of  this  chloride  apparently 
yielded  about  110  parts  of  its  elements  uranium  and  chlorine.  His  ex 
planation  of  this  seemingly  impossible  result  was  that  the  uranous  chloride 
reacts  with  water  in  the  following  manner: 

UC14  +  2H2O  =  UO2  +  4HC1 

Since  uranous  oxide  cannot  be  reduced  with  hydrogen  or  carbon,  it  had 
always  been  mistaken  for  metallic  uranium. 

Peligot  then  heated  the  anhydrous  chloride  with  potassium  in  a 
closed  platinum  crucible.  This  was  heroic  treatment  for  the  platinum, 
to  be  sure,  for  the  reaction  was  violent  enough  to  make  crucible  and 
contents  white-hot.  However,  since  he  took  care  to  place  the  small 


268  DISCOVERY  OF  THE  ELEMENTS 

crucible  inside  a  larger  one  and  to  remove  his  alcohol  lamp  as  soon 
as  the  reaction  had  started,  Peligot  avoided  being  injured  by  the  pieces 
of  potassium  thrown  out  of  the  crucible.  When  the  violent  reaction  sub- 


iiiiii 


From  FercU's  "Von  Libau  bis  Liebig" 


The  Rose  Pharmacy  in  Berlin.*  Valentin  Rose  the  Elder 
(1735-1771),  his  son  Valentin  Rose  the  Younger  (1762- 
1807),  and  his  grandson  Heinrich  Rose  (1795-1864)  all 
rendered  distinguished  service  to  chemistry  and  pharmacy. 


sided,  he  heated  the  crucible  strongly  to  remove  the  excess  potassium 
and  to  make  the  reduced  uranium  coherent.  After  cooling  it,  he  dis 
solved  out  the  potassium  chloride,  and  obtained  a  black  metallic  powder 
with  properties  quite  different  from  those  formerly  attributed  to  metallic 
uranium  (15,  31).  He  was  evidently  the  first  person  to  isolate  this  metal. 

*  Reproduced  by  courtesy  of  Mr.  Arthur  Nemayer,  Buchdruckerei  und  Verlag, 
Mittenwaldy  Bavaria, 


CHROMIUM,  MOLYBDENUM,  TUNGSTEN,  URANIUM 


269 


Eugene-Melchior  Peligot  was  bom  on  February  24,  1811,  at  Paris. 
He  studied  at  the  Lycee  Henri  IV  and  at  the  Central  School  of  Arts  and 
Manufactures,  but  was  obliged  to  leave  school  for  financial  reasons.  In 
1832,  however,  good  fortune  dawned  for  him,  and  he  was  admitted  to 
the  laboratory  of  the  Ecole  Polytechnique  to  study  under  J.-B.  Dumas. 
A  few  years  later  he  was  collaborating  with  Dumas  in  important  re 
searches  in  organic  chemistry. 

For  thirty-five  consecutive  years  Peligot  occupied  the  chairs  of 
analytical  chemistry  and  glassmaking  at  the  Central  School  of  Arts  and 
Manufactures,  and  during  this  time  he  wrote  an  important  treatise  on 
each  of  these  subjects.  He.  also  lectured  to  large,  sympathetic  audiences 
at  the  Conservatoire  des  Arts  et  Metiers,  and  taught  a  course  in  agri 
cultural  chemical  analysis  at  the  National  Agronomic  Institute. 


Eugene  Peligot,  1811-1890.  Professor 
of  analytical  chemistry  and  glassmaking 
at  the  Central  School  of  Arts  and  Manu 
factures  in  Paris.  Director  of  assays  at 
the  Paris  Mint.  Professor  of  agricultural 
chemical  analysis  at  the  National  Agro 
nomic  Institute.  The  first  to  isolate  the 
metal  uranium. 


He  was  employed  at  the  Mint  for  forty  years,  first  as  assayer,  then 
as  verifier,  and  finally  as  Director  of  Assays.  His  residence  was  at  the 
Mint  also,  and  it  was  there  that  he  died  in  1890.  According  to  Tis- 
sandier,  "his  life,  always  calm  and  methodical,  was  entirely  consecrated 
to  the  science  that  he  loved  with  passion  and  to  his  family  that  he 
cherished  no  less"  (34).  He  must  have  been  a  man  of  broad  interests, 
for  he  published  papers  on  such  varied  topics  as:  water  analysis,  the 


270 


DISCOVERY  OF  THE  ELEMENTS 


chemical  composition  of  the  sugar  beet  and  sugar  cane,  chemical  and 
physiological  studies  of  silkworms,  the  composition  of  Bohemian  glass, 
and  researches  on  uranium  and  chromium  (6). 


?///•;  merits  of  KL, I /Vt*O  7  //,  ///  t  'ht,iiH'<tf  An<i- 
/#//>•,  arc  Jt)  cHiiutnlh}  ^ridl>liflnd  n't  fit  men  r/ 
fcience  throughout  A'j/ro/v,  tfmf  it  i£t)u!d  jeem  //«- 
prapcr  to  enlarge  mi  thr  majt  roiijtimmttlcjLili  ttn<f 
ticcitraiy  with  &•///*'//  he  fu,>rfnriut'*l  ft  in  t;t/s<Tit'tt'ttt,tt 
as  ur#  tfi'  uti  his  hititiahU'  catutvurinjluitng  their 
refuttJ. 

On  l/tfjt  caufitleratwut  it  ^  tntjtti  that  tin'  Irtuif* 
fatton  qf  his  Atnlytico-chcmicnl  JUHijs,  tir.ttktt'h 
f.t  htre  offli't  d  A*  th?  jwfraa'W  vf  the  Knglijk 
Cheat yfs*  ^ittwcrt  i<:i^i  thrir  f.nu£  Gtfywbathnf-?- 
tt  may  be  ntcejjbrtt  tit  «,&/,  tlmt  till  the  Eiliiys  of 
Ihi'  .luther  relating  to  thi$  Juliet,  ami  iJifcht  m 
ike  German  origitial,  i^ar  inihlfjhcd  hi  UM  vvlumw* 
firc,Jt}y  the  ttcc&ntinvilrittvtt  i*f  the  pub  lie  *  i\twprn~ 
cd in  fhixjtngtt'  ['flu tut:, 

Wffrneiw  Mr.  Klaprvtls*  */*  1w  hay  v^vcn  ftopt-s 
to  tkf  Trtwjl(ttttry  Jfattt  giw another  fo/Uctioa  vf 
A/v  /t///  tttnJ  mwjl  }\tfa$$t  they  will  be  unMeilfafefy 
reiificf'fil  in  ft)  Kjti*hjh, 

f"7  If  fins*  ty$>i,£riipktt«I  rrttr  ,  a»J  <jf,  w  etitif  iKi/ln^i 
tihkli  HKfMnti&tffy  buiif  y<.tip<d  th  myl  <.«'-///  uttw&n* 
fh-ttH  ctmUJsMf  tliji?i*icltf,  >/•/'<•  JtftJ  "•;.  *><  '..,,/ffJj  rf^Nti'i.  t 
'<  rtfir  ij  fli~  et'f&u  in  t/w  t*i/}  pn^  <•'. 


Translator's  Preface  to  the 
English  Edition  of  Klaproth's 
"Analytical  Essays  towards 
Promoting  the  Chemical 
Knowledge  of  Mineral  Sub 
stances" 


Uranium  in  Mineral  Waters.  In  1929  A.  Pereira-Forjas  demon 
strated  the  presence  of  uranium  in  the  mineral  water  from  Cambres, 
Corredoura,  Portugal.  He  detected  it  spectroscopically  in  the  water 
itself,  not  in  the  residue  (78,79).  M.  Herculano  de  Carvalho  found  that 
the  uranium  in  five  springs  near  Caria,  Casteleiro,  Portugal,  after  sepa 
ration  of  the  radium,  amounted  to  10~6  gram  per  liter  (80). 


CHROMIUM 

Nicolas-Louis*  Vauquelin,  the  discoverer  of  the  metal  chromium, 
was  born  on  May  16,  1763,  in  a  little  Normany  village  called  St.  Andre 

*  In  the  Annuaire  of  the  Academic  des  Sciences  the  names  are  given  thus,  not  in  the 
reverse  order. 


CHROMIUM,  MOLYBDENUM,  TUNGSTEN,  URANKJM  271 

d'Hebertot*  As  a  child  he  worked  in  the  fields  with  his  father,  who 
struggled  hard  to  feed  and  clothe  his  large  family.  The  boy  made  sur 
prisingly  rapid  progress  in  the  village  school  and  in  the  religious  studies 
taught  him  by  the  cure,  who  was  very  fond  of  him  (16).  At  the  age  of 
fourteen  years,  young  Vauquelin  became  a  laboratory  assistant  and  dish 
washer  in  an  apothecary  shop  in  Rouen,  and  somewhat  later  he  went 
to  Paris  with  a  letter  of  introduction  from  his  old  cure  at  St.  Andre 
d'Hebertot  to  the  prior  of  the  order  of  Premontre.  His  two  best  friends 
during  his  early  struggles  in  Paris  were  this  venerable  prior  and  Mme. 
Aguesseau,  the  owner  of  the  estate  on  which  the  elder  Vauquelin  worked 
as  a  peasant  (16). 


Nicolas-Louis     Vauquelin,     1763-1829. 

French  analytical  and  mineralogical 
chemist  and  apothecary  of  the  Revolu 
tionary  Period.  Professor  at  the  ficole 
Polytechnique  and  at  the  School  of 
Mines.  Assayer  at  the  Paris  Mint.  In 
1797  he  discovered  chromium  and  in 
1798  beryllium. 


During  his  first  three  years  in  the  city,  the  boy  worked  in  various 
apothecary  shops,  and  in  his  leisure  moments  studied  Latin  and  botany. 
One  of  these  pharmacies  was  owned  by  M.  Cheradame,  a  cousin  of  the 
famous  chemist,  Antoine-Frangois  de  Fourcroy.  When  M.  Cheradame 
told  Fourcroy  about  young  Vauquelin's  fondness  for  chemistry,  Fourcroy 
immediately  engaged  the  boy  as  his  assistant  and  took  him  home.  Four- 
croy's  unmarried  sisters  treated  the  young  assistant  with  all  gentleness  and 
kindness,  and  on  one  occasion  he  owed  his  recovery  from  a  serious  illness 
to  their  motherly  care,  an  act  of  kindness  which  he  never  forgot, 

*  Also  spelled  Saint- Andre  des  Berteaux. 


272  DISCOVERY  OF  THE  ELEMENTS 

Vauquelin  continued  his  study  of  physics,  chemistry,  and  philosophy, 
and  assisted  Fourcroy  in  teaching  a  course  at  the  Athenaeum.  He  was 
diffident  about  speaking  in  public,  but  as  soon  as  he  became  acquainted 
with  his  new  students,  he  always  taught  with  pleasure  and  enthusiasm 
and  soon  endeared  himself  to  them. 

One  of  the  stirring  events  of  the  Revolution  was  Vauquelin's  rescue, 
from  the  mob,  of  an  unfortunate  Swiss  soldier  who  had  escaped 
from  the  Tuileries  massacre.  Because  of  his  participation  in  the  Revolu 
tion,  Vauquelin  had  to  leave  Paris  in  1793;  however,  after  serving  as 
pharmacist  in  a  military  hospital  for  a  few  months,  he  returned  to  Paris 
to  teach  chemistry  at  the  Central  School  of  Public  Works,  which  after 
ward  became  the  Ecole  Polytechnique.  He  later  became  an  inspector 
of  mines  and  professor  of  assaying  at  the  School  of  Mines,  where  he  also 
lived.  Out  of  gratitude  to  Fourcroy's  sisters,  who  continued  to  keep 
house  for  him  even  after  the  death  of  their  brother,  Vauquelin  placed 
most  of  the  apartment  at  their  disposal,  and  both  the  sisters  lived  with 
him  until  they  died  (16,  35). 

The  first  analysis  of  the  Siberian  red  lead  (crocoite  or  crocoisite) 
which  M.  V.  Lomonosov  (1711-1765)  had  described  was  made  by  Johann 
Gottlob  Lehmann  in  1766  (43,  96).  He  was  highly  esteemed  as  director 
of  the  Prussian  mines  and  as  a  lecturer  in  Berlin.  In  1761  he  became  pro 
fessor  of  chemistry  and  director  of  the  Royal  Museum  in  St.  Petersburg, 
and  was  commissioned  by  Catherine  II  to  make  extensive  mineralogical 
trips  throughout  the  Russian  Empire.  He  described  the  Siberian  red 
lead  in  a  letter  to  the  Comte  de  Buffon  in  1766.  At  that  time  it  was 
found  only  at  a  smelter  fifteen  versts  from  Ekaterinenstadt  (Marxstadt). 
In  his  chemical  investigation  of  it,  Lehmann  dissolved  it  in  hydrochloric 
acid,  noticed  the  emerald-green  color  of  its  (reduced)  solution,  and 
found  that  the  mineral  contained  lead.  He  concluded  that  it  must  be  "a 
lead  mineralized  with  a  selenitic  spar  and  iron  particles"  (44).  In  1767 
his  life  was  suddenly  cut  short  by  the  bursting  of  a  retort  in  which  he 
was  heating  some  arsenic  (45). 

In  1770  P.  S.  Pallas  described  the  Beresof  gold  mines  near  Ekaterin 
burg  (Sverdlovsk),  Siberia.  On  the  25th  and  26th  of  June  of  that  year 
he  wrote:  "The  Beresof  pits  include  four  mines,  which  have  been  worked 
since  1752."  The  Beresof  mine  also  yielded  copper,  lead,  and  silver. 
"A  very  remarkable  red  lead  mineral  is  also  exploited  there,"  said  Pallas, 
"which  has  never  been  found  in  any  other  mine  of  the  Empire  or  else 
where.  This  lead  ore  is  heavy,  of  varying  color  (sometimes  like  that  of 
cinnabar),  and  semi-transparent.  .  .  .  One  also  finds  small  irregular, 
tortuous  pyramids  of  it  attached  like  little  rubies  to  quartz.  When 
pulverized,  it  gives  a  handsome  yellow  guhr  which  could  be  used  in 


CHROMIUM,  MOLYBDENXTM,  TUNGSTEN,  UBANIUM  273 

miniature  painting.  ...  It  is  difficult  today  to  procure  enough  of  it  for 
large-scale  assays,  for  the  part  of  the  mine  where  this  lead  ore  is  found 
is  seldom  worked,  for  lack  of  air.  .  .  .  Five  hundred  workmen  are  now 
employed  in  these  mines  .  .  ."  (46). 

Peter  Simon  Pallas  (1741-1811)  was  a  native  of  Berlin.  He  was 
broadly  educated  in  medicine,  natural  sciences,  and  modern  languages, 
which  he  studied  in  Berlin,  Halle,  Gottingen,  the  Netherlands,  and  Eng 
land.  From  1768  until  1774  he  made  extended  journeys  at  the  request 
of  Catherine  II  and  suffered  great  privations  in  order  to  study  the 
natural  history  of  Siberia,  the  Altai  Mountains,  the  lower  Volga  region, 
and  the  southern  part  of  European  Russia  (47,  48,  49). 

In  1797-98  N.-L.  Vauquelin  analyzed  crocoite  and  gave  a  detailed 
account  of  its  history.  "Ah1  the  specimens  of  this  substance  which  are  to 
be  found  in  the  several  mineralogical  cabinets  in  Europe,"  said  he,  "were 
obtained  from  this  [Beresof]  gold  mine;  which  indicates  that  it  was 


Antoine-Fransois  de  Fourcroy,  1755- 
1809.  French  chemist  of  the  Revolu 
tionary  Period.  Defender  of  Lavoisier's 
views  on  combustion.  In  collaboration 
with  Lavoisier,  Guyton  de  Morveau, 
and  Berthollet  he  carried  out  a  reform 
of  chemical  nomenclature.  Fourcroy 
prepared  and  analyzed  many  reagents 
and  medicinals. 


formerly  abundant;  but  it  is  said  that  for  some  years  past  it  has  become 
very  scarce,  and  that  at  present  it  is  bought  for  its  weight  in  gold,  es 
pecially  if  pure  and  regularly  formed.  The  specimens  which  do  not 
possess  the  regular  figure,  or  are  broken  into  fragments,  are  appropriated 
to  painting,  in  which  art  this  substance  is  of  high  value  for  its  beautiful 
orange-yellow  colour,  its  unchangeableness  in  the  air,  and  the  facility 
with  which  it  can  be  levigated  with  oil"  (36). 

"The  beautiful  red  colour,  transparency,  and  crystalline  figure  of 
the  Siberian  red  lead,"  continued  Vauquelin,  "soon  induced  mineralogists 


274  DISCOVERY  OF  THE  ELEMENTS 

and  chemists  to  make  enquiries  into  its  nature.  The  place  of  its  dis 
covery,  its  specific  gravity,  and  the  lead  ore  which  accompanies  it 
produced  an  immediate  suspicion  of  the  presence  of  that  metal;  but,  as 
lead  had  never  been  found  in  possession  of  the  characteristic  properties 
of  this  Siberian  ore,  they  thought,  with  justice,  that  it  was  mineralised  by 
some  other  substance;  and  Lehmann,  who  first  subjected  it  to  chemical 


Peter  Simon  Pallas,  1741-1811.  Ger 
man  scientist  who  made  extensive  sci 
entific  journeys  to  study  the  natural 
history  of  Russia  and  Siberia.  He  de 
scribed  the  Beresof  gold  mines  and  the 
"Siberian  red  lead"  (crocoite)  in  1770. 


The  Naturalist's  Library,  Vol.  9 

analysis,  asserted,  in  a  Latin  dissertation  printed  at  Petersburgh  in  1766 
that  the  mineralisers  were  arsenic  and  sulphur"  (36).     When  Vau 
quelin  and  Macquart  analyzed  it,  they  found  it  to  consist  of  lead  peroxide, 
iron,  and  aluminum.     Bindheim  of  Moscow  reported,  however,  that  it 


Fourcroy   Autograph  from 

his  "System e  des  Connais- 

sances  Chimiques." 


Oefr  onvrage  09*  mis  sous  \&  sanve-gartU  <!e  ia  t« 
Tons  Ics  oxempkurcs  sent  signes  par  I'Auteur  et  TJ 


contained  molybdic  acid,  nickel,  cobalt,  iron,  and  copper.    To  settle  this 
question  Vauquelin  in  1797  repeated  the  analysis  (32). 

"My  labours  (said  Vauquelin)  have  not  been  without  their  recom 
pense;  and  I  hope  to  prove  in  the  following  paragraphs  that  all  which 


CHROMIUM,  MOLYBDENUM,  TUNGSTEN,  URANIUM  275 

has  hitherto  been  asserted  with  regard  to  the  mineraliser  of  the  Siberian 
red  lead  is  entirely  destitute  of  foundation;  that  it  contains  neither  arsenic, 
as  Lehmann  pretended;  nor  the  molybdic  acid  and  the  three  or  four 
metals  as  announced  by  Bindheim;  nor  iron  nor  clay,  as  Macquart  and 
myself  imagined;  but  a  new  metal,  possessing  properties  entirely  unlike 
those  of  any  other  metal  .  .  ."  (36,  81).  When  Vauquelin  boiled  the 


Dedication    of    the    German 

Edition    of    Scheele's    Works 

Edited  by  Hermbstadt 


SK.  WOHLGKBOJIKXFN 


H    E    H    R    N 

MARTIN    HEINRICH 
KLAPROTH, 

i*r»f«2br  der  Ch«m«  bey  der  JUjnigl.  I*  reals.  Aitilleiie-  Akatlenii*, 

AffdfTor  PJiarmacie  bty  dem  KSfligl.  Obercollegio-  medico,  Mjtghed 

der  35,emgl.  Prtiif**  Akademie  der  "Wififenfchaften  f    wit  aufji  tie* 

Akadenue  der  Kunfl*  un4  mtch^wfchen  WiSeatoaft«n  zu  Berlin; 

der  Churftir!ll»  Mayor,  Afcademie  der  Wifieufchaftco  ?u  Erfurt  *  tier 

naiur&rfchenden  Gefellfchift  zu  Berlin  und  Halls;  imglcicfeen 

d«r  Societal  der  Retgbaukuade,  unJ  ynvilegirter' 

Apothek«r  ?u,  B*f!in  etc. 

als  «inen   Jclelnen  Begets 

feiner  gegriindeten  Hochachtuhg,  JLiebe  uftd 
wahren  Veiehrung 


von    dem   Herausgeber. 


pulverized  mineral  with  two  parts  of  potassium  carbonate,  he  obtained 
lead  carbonate  and  a  yellow  solution  containing  the  potassium  salt  of 
an  unknown  acid.  This  solution  gave  a  beautiful  red  precipitate  when 
added  to  the  solution  of  a  mercuric  salt  and  a  yellow  precipitate  when 
added  to  a  lead  solution.  He  noticed  also  that  when  he  isolated  the 
new  acid  and  added  stannous  chloride,  the  solution  became  green  (re 
duction  of  chromic  acid  to  a  chromic  salt)  (17). 


276  DISCOVERY  OF  THE  ELEMENTS 

In  1798  Vauquelin  succeeded  in  isolating  the  new  metal.  After 
removing  the  lead  in  the  Siberian  red  lead  by  precipitation  with  hydro 
chloric  acid,  he  evaporated  the  filtrate  to  obtain  the  chromium  trioxide, 
which  he  put  into  a  charcoal  crucible  placed  inside  a  large  earthen  one 
filled  with  charcoal  dust.  After  heating  it  intensely  for  half  an  hour, 
he  allowed  it  to  cool.  The  inner  crucible  was  found  to  be  filled  with  a 
network  of  gray,  interlacing  metallic  needles  which  weighed  one-third 
as  much  as  the  original  chromium  trioxide  that  had  been  reduced.  Be 
cause  of  its  many  colored  compounds  Fourcroy  and  Haiiy  suggested  the 
name  chromium  for  the  new  metal  (17,  36). 

Vauquelin  taught  for  a  time  at  the  College  de  France  and  at  the 
Jardin  des  Plantes,  and  in  1811,  upon  the  death  of  his  old  friend  and 
teacher,  M.  Fourcroy,  he  became  his  successor  as  professor  of  chemistry 
in  the  School  of  Medicine.  In  1828  the  Department  of  Calvados,  in 
which  his  native  village  of  St.  Andre  d'Hebertot  is  situated,  appointed 
him  as  one  of  its  deputies.  He  discharged  the  duties  of  this  office  with 
honor,  striving  always  for  the  best  interest  of  his  beloved  Republic. 
Although  his  early  days  were  spent  in  poverty  and  toil,  he  became  a 
man  of  broad  culture.,  took  pleasure  in  music  and  literature,  and  fre 
quently  quoted  his  favorite  authors,  Horace  and  Virgil  (16). 

M.  Chevallier,  one  of  his  students,  recalled  an  incident  that  well 
illustrates  Professor  Vauquelin's  kindness.  In  1808  Bonaparte  ordered 
the  arrest  and  deportation  of  all  Spaniards  living  in  Paris.  One  of  the 
sixty  who  were  seized  and  taken  to  the  prefecture  of  police  was  a  young 
man  who  had  recently  come  to  study  under  Professor  Vauquelin  and 
who  had  no  other  protector  in  Paris.  Vauquelin  started  out  before  six 
o'clock  next  morning,  dressed  in  the  uniform  worn  on  formal  occasions 
by  members  of  the  Institute,  went  to  the  police  station,  and  succeeded  in 
having  the  boy  released.  The  young  Spaniard,  who  was  named  Mateo 
Jose  Buenaventura  Orfila,  afterward  made  a  great  name  for  himself  in 
chemistry  (16,35,66). 

Sir  Humphry  Davy  once  gave  the  following  amusing  description  of 
Vauquelin's  home  life: 

Vauquelin  was  in  the  decline  of  life  when  I  first  saw  him  in  1813— a  man 
who  gave  me  the  idea  of  the  French  chemists  of  another  age;  belonging  rather 
to  the  pharmaceutical  laboratory  than  to  the  philosophical  one;  yet  he  lived  in 
the  Jardin  du  Roi.  Nothing  could  be  more  singular  than  his  manners,  his  life, 
and  his  menage.  Two  old  maiden  ladies,  the  Mademoiselles  de  Fourcroy,  sisters 
of  the  professor  of  that  name,  kept  his  house.  I  remember  the  first  time  that  I 
entered  it,  I  was  ushered  into  a  sort  of  bed-chamber,  which  likewise  served  as  a 
drawing-room.  One  of  the  ladies  was  in  bed,  but  employed  in  preparations  for 
the  kitchen;  and  was  actually  paring  truffles.  Vauquelin  wished  some  imme- 


CHROMIUM,  MOLYBDENUM,  TUNGSTEN,  URANIUM  277 

diately  to  be  dressed  for  my  breakfast,  and  I  Had  some  difficulty  to  prevent 
it.  .  .  (18). 

This  was,  to  be  sure,  an  unusual  way  of  receiving  a  fashionable  English 
gentleman,  but  perhaps  if  Sir  Humphry  had  known  the  pleasing  story 
of  Vauquelin's  gratitude  to  the  two  old  ladies  who  had  befriended  him 
in  youth,  he  would  not  have  been  so  critical. 

Vauquelin  in  France  and  Klaproth  in  Germany  were  the  outstanding 
analytical  chemists  of  their  day,  and  were,  in  fact,  two  of  the  greatest 


Mathieu  -  Joseph  -  Bonaventure  Orfila, 
1787-1853.  Spanish  chemist  who 
studied  under  Vauquelin  in  Paris.  The 
founder  of  modern  toxicology.  Profes 
sor  of  toxicology,  medical  chemistry, 
and  forensic  chemistry  in  Paris. 


analysts  of  all  time.  According  to  Thomson,  Vauquelin  was  "by  far 
the  most  industrious  of  all  French  chemists  (19).  He  died  in  his  native 
district  at  the  Chateau  des  Berteaux  on  November  14,  1829. 

Among  the  other  early  investigators  of  crocoite  (Siberian  red  lead) 
were  Count  Apollos  Apollosovich  Musin-Pushkin*  (1760-1805),  Tobias 
Lowitz  (Tovii  Egorovich  Lovits)  (1757-1804),  and  M.  H.  Klaproth  (82}. 
Count  Musin-Pushkin's  analyses  were  made  with  portable  equipment 
during  one  of  his  mineralogical  journeys  (82). 

This  handsome  mineral  has  also  been  found  in  Brazil,  Hungary,  the 
Philippine  Islands,  Arizona,  and  Tasmania.  The  Academy  of  Natural 
Sciences  of  Philadelphia  has  some  superb  specimens  of  it  from  Dundas, 
Tasmania. 

*  In  the  literature  one  often  finds  this  name  transliterated  as  Moussin-Puschldn. 


278  DISCOVERY  OF  THE  ELEMENTS 

Chromium  in  the  Emerald  and  the  Ruby.  When  Vauquelin  analyzed 
a  Peruvian  emerald  in  1798  he  found  that  its  green  color  was  caused  by 
the  presence  in  it  of  a  small  amount  of  chromium.  By  boiling  some  of 
the  coloring  matter  from  the  emerald  with  concentrated  nitric  acid, 
evaporating  the  solution  to  dryness,  and  adding  caustic  potash  to  the 
residue,  he  obtained  a  yellow  solution  which  when  treated  with  lead 
nitrate  solution  "immediately  regenerated  the  red  lead  of  Siberia"  (83), 

The  red  color  of  the  ruby  is  also  caused  by  the  presence  in  it  of  a 
trace  of  chromic  oxide,  which  distinguishes  this  costly  gem  from  common 
crystalline  corundum  (alumina).  Thus  chromic  oxide,  according  to 
F.  H.  Pough,  "is  the  most  valuable  commodity  in  the  world  when  pur 
chased  in  the  form  of  a  ruby"  (84).  A  beautifully  illustrated  article  on 
synthetic  rubies  appeared  in  the  Journal  of  Chemical  Education  for  June, 
1931  (85). 

Chromite.  In  a  letter  to  Scherer's  Journal,  dated  St.  Petersburg, 
November  12,  1798,  Count  Musin-Pushkin  wrote:  "You  already  know 
that  Mr.  Lowitz  and  Mr.  Klaproth  have  independently  discovered 
chromium  combined  with  iron  in  a  fossil  I  sent  them.  This  ore  looks 
like  the  black  uranium  ore  (pitchblende),  but  has  a  more  metallic  luster" 
(87).  In  the  same  year  Mining  Superintendent  von  Soymonof  had 
found  some  of  this  mineral  in  the  northern  part  of  the  Ural  Mountains. 
When  Lowitz  analyzed  it,  he  concluded  that  it  must  be  iron  chromate 
(88), 

Tobias  Lowitz  (Tovii  Egorovich  Lovits)  was  born  at  Gottingen  in 
1757.  When  he  was  ten  years  old,  his  father  was  called  to  St.  Petersburg 
as  a  professor  of  mathematics  and  member  of  the  Imperial  Academy  of 
Sciences  (92).  After  serving  as  an  apprentice  in  the  Royal  Apothecary 
in  St.  Petersburg,  and  after  further  study  in  chemistry  and  pharmacy  at 
Gottingen,  Tobias  Lowitz  finally  became  a  member  of  the  Russian 
Academy  of  Sciences  as  successor  to  M.  V.  Lomonosov.  He  carried  out 
many  successful  researches  on  the  adsorption  of  dissolved  substances 
by  wood  charcoal,  crystallography,  freezing-mixtures,  and  other  branches 
of  analytical,  physical,  and  organic  chemistry.  In  1789,  in  the  course  of 
some  experiments  on  crystallization,  he  discovered  glacial  acetic  acid 
(86).  While  studying  chromium  he  lost  his  left  hand  in  a  laboratory 
accident.  After  a  long  illness  he  died  at  St.  Petersburg  in  1804. 

In  1799  Citizen  Tassaert,  a  Prussian  chemist  who  had  been  working 
for  several  years  at  the  School  of  Mines  of  Paris,  discovered  chromium 
in  an  iron  mineral  found  at  the  Carrade  Villa  near  Gassin  in  the  depart 
ment  of  du  Var.  He  too  regarded  the  mineral  as  a  chromate  of  iron  (89 ) . 
Since  chromium  had  previously  been  detected  in  the  "red  lead  of  Siberia" 
(crocoite),  in  the  emerald,  and  in  the  ruby,  the  chrome-iron  mineral 


CHROMIUM,  MOLYBDENUM,  TUNGSTEN,  URANIUM  279 

analyzed  by  Tassaert  and  by  Lowitz  was  the  fourth  substance  found  to 
contain  this  recently  discovered  metal. 

Fourcroy  predicted  that  this  mineral  would  give  chemists  the  op 
portunity  to  make  a  more  thorough  study  of  the  properties  of  chromium 
and  perhaps  to  discover  compounds  of  it  which,  because  of  their  rich 
and  varied  colors,  would  be  useful  in  painting  and  in  the  manufacture 
of  glass  and  enamel  (90).  He  also  encouraged  study  of  the  chromium 
alloys.  The  chrome-iron  ore  is  now  known  as  chromite.  It  is  not  a 
chroma te,  but  has  the  spinel  composition,  Fe  ( CrO2 )  2- 

Chromium  in  Meteorites.  In  1817  Andre  Laugier  detected  chromium 
and  sulfur  in  the  great  Pallas  meteorite  from  Siberia.  Earlier  analysts 
had  reported  only  iron  and  nickel  (91). 

Chromium  has  taken  its  place  among  the  world's  useful  metals,  and 
stainless  steel,  chromium-plated  hardware  and  automobile  trimmings,  and 
artistic  chromium  jewelry  now  bear  witness  to  the  importance  of  Vau- 
quelin's  discovery. 

LITERATURE  CITED 

(1 )  VALLERY-RABOT,  R.,  "Life  of  Pasteur,"  English  translation  by  Mrs.  Devonshire, 

Doubleday,  Page  and  Co.,  New  York,  1928,  p.  152. 

(2)  JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  Vol.  2,  Baudry  et  Cie.,  Paris,   1891, 

pp.  344-5. 

(3)  NORDENSKIOLD,  A.  E.,  "C.  W.  Scheele's  nachgelassene  Briefe  und  Aufzeich- 

nungen,"  Norstedt  &  Soner,  Stockholm,  1892,  pp.  362-3. 

(4)  Ibid.,  p.  370. 

(5)  DEL  Rio,  A.  M.,  "Analysis  of  an  alloy  of  gold  and  rhodium  from  the  parting 

house  at  Mexico,"  Annals  of  Phil,  10,  256  (Oct.,  1825). 

(6)  POGGENDORFF,  J.  C.,  "Biographisch-Literarisches  Handworterbuch  zur  Geschi- 

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(7)  NORDENSEIOLD,  A.  E.,  "Scheele's  nachgelassene  Briefe  und  Aufzeichnungen," 

ref.  (3),  pp.  373-4. 

(8)  Ibid.,  pp.  332,  399-400. 

(9)  Ibid.,  p.  389.    Letter  of  Mar.  13,  1780. 

(10)  Ibid.,  p.  381. 

(11)  THOMSON,  THOMAS,   "History  of  Chemistry,"  Vol.   2,  Colburn  and  Bentley, 

London,  1931,  pp.  192-3;  FERGUSON,  ELSIE  G.,  "Bergman,  Klaproth,  Vau- 
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p.  65. 

(13)  BUGGE,  G.,  "Das  Buch  der  grossen  Chemiker,"  Vol.  1,  Verlag  Chemie,  Berlin, 

1929,  p.  334. 

(14)  THOMSON,  THOMAS,  "History  of  Chemistry,"  ref.  (11),  Vol.  2,  pp.  197-8. 

(15)  JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  ref.  (2),  Vol.  2,  pp.  322-4. 

(16)  "Biographic  Universelle,  Ancienne  et  Moderne,"   85  vols.,   Michaud   Freres, 

Paris,  1813.    Article  on  Vauquelin  by  Chevallier. 

(17)  JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  ref.  (2),    Vol.  2,  pp.  317-8. 

(18)  DAVY,  DR.  JOHN,  "Memoirs  of  the  Life  of  Sir  Humphry  Davy,  Bart.,"  Smith, 

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280  DISCOVERY  OF  THE  ELEMENTS 

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(89)  TASSAERT,  "Chemische  Zerlegung  des  chromiumsauren  Eisens   (chromiate  de 

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CHROMIUM,   MOLYBDENUM,  TUNGSTEN,  URANIUM  283 

(93)  SYKES,  W.  P.,  "Metallurgy  of  tungsten  and  molybdenum/'  Ibid.,  17,  190-2 

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(Jourtesy  Dr.  Moles  and  Mr.  de 

Fausto  de  Elhuyar,  1 755-1 833,  as  he  appeared  while 
studying  in  Vienna  before  going  to  Mexico,  At  this 
period  he  was  already  famous  because  of  the  research 
at  Vergara  in  which  he  and  his  brother  liberated  the 
element  now  known  as  tungsten  (wolfram).  This  por 
trait  was  bequeathed  to  the  Mining  Council  by  Don 
Fausto's  daughter.  Dona  Luisa  de  Elhuyar  de  Martinez 

de  Aragon. 


10 


Contributions  of  the  de  Elhuyar  brothers 


Although  Don  Fausto  de  Elhuyar  and  his  brother,  Don  Juan 
Jose,  achieved  undying  fame  by  their  isolation  of  the  element  now 
known  as  tungsten  (wolfram),  only  meager  accounts  of  their 
contributions  have  been  recorded  in  the  English  language,  and 
even  in  Spanish  and  Spanish-American  journals  it  is  difficult  to 
find  more  than  brief  mention  of  Don  Juan  Jose.  This  Castilian 
literature,  however,  contains  a  wealth  of  information  about  the 
scientific  activities  of  Don  Fausto,  and  the  observance  of  the 
centenary  of  his  death  brought  forth  new  biographical  material. 


L 


.n  the  latter  part  of  the  eighteenth  century  the  Count  of  Pena- 
florida,  with  the  approval  of  King  Charles  III,  founded  in  the  Basque 
provinces  a  patriotic  organization  known  as  "The  Basque  Society  of 
Friends  of  their  Country"  (Sociedad  Vascongada  de  Amigos  del  Pais}. 
In  the  early  days  of  its  existence,  this  learned  society,  consisting  of 
studious  men  of  the  nobility  and  clergy,  used  to  meet  every  evening  in 
the  week.  On  Mondays  they  discussed  mathematics;  on  Tuesdays  they 
made  experiments  with  Abbe  Nollet's  electrical  machine  or  with  their 
air  pump  from  London  or  discussed  the  physical  theories  of  the  day, 
such  as  Franklin's  views  on  electricity;  on  Wednesdays  they  read  history 
and  translations  by  members  of  the  society;  on  Thursdays  they  listened  to 
music;  on  Fridays  they  studied  geography;  on  Saturdays  they  conversed 
on  current  events;  and  on  Sundays  they  again  listened  to  music.  Accord 
ing  to  a  contemporary  writer,  Don  Juan  Sempere  y  Guarinos  (1): 

The  two  most  glorious  monuments  of  the  Sociedad  Vascongada  are  the 
Seminary  of  Vergara  and  the  House  of  Mercy  of  Vitoria.  .  .  .  This  Seminary 
was  the  first  in  Spain  in  which  virtue  was  united  with  the  teaching  of  the  sci 
ences  most  useful  to  the  state.  Vergara  was  the  first  town  in  which  chairs  of 
chemistry  and  metallurgy  were  founded. 

Soon  after  this  Seminary  was  founded  in  1777,  two  brilliant  and 
promising  youths  of  Basque  and  French  lineage,  Don  Juan  Jose  de 
Elhuyar  y  de  Zubice  (1754-1796)  and  his  younger  brother,  Don  Fausto, 
were  commissioned  to  study  abroad.  Don  Juan  Jos6  was  sent  by  the  King 

285 


286 


DISCOVERY  OF  THE  ELEMENTS 


to  master  the  science  of  metallurgy  and  Don  Fausto  was  chosen  by  the 
Count  of  Penaflorida  to  study  mineralogy  at  the  expense  of  the  Society 
of  Friends  of  their  Country  and  become  the  first  professor  of  that  sub 
ject  at  the  new  Seminary  (2). 

Don  Fausto  was  bom  at  Logrono  in  northern  Spain  on  October  11, 
1755,  and  was  educated  in  Paris  under  the  best  masters.    While  the  gifted 


Courtesy  Dr.  Moles  and  Mr.  de  Gdlvez-Canero 


The  Seminary  of  Vergara.  It  was  here  that  Don  Juan  Jose  and  Don  Fausto 
de  Elhuyar  carried  out  their  remarkable  analysis  of  wolframite,  which 
resulted  in  the  isolation  of  a  new  metal,  "wolfram,"  or  tungsten.  Among 
the  professors  at  this  Seminary  were  L.-J.  Proust,  Frangois  Chabaneau,  and 
Fausto  de  Elhuyar.* 


young  Louis-Joseph  Proust  (3),  who  later  defended  the  law  of  definite 
proportions  so  valiantly  against  C.-L.  Berthollet,  taught  chemistry  at 
Vergara,  Don  Fausto  and  Don  Juan  Jose  went  to  Freiberg,  where  in  1778 
they  enrolled  as  students  in  the  Royal  School  of  Mines,  studied  subter 
ranean  geometry,  mining,  metallurgy,  and  machine  construction,  and 
became  ardent  disciples  of  the  great  mineralogist  Abraham  Gottlob 
Werner.  Don  Juan  Jose  profited  from  December  1781  to  July  1782  by 
a  brief  course  of  study  at  Upsala  under  the  celebrated  Torbern  Bergman. 

*  Even  in  Spanish  literature,  the  spelling  of  this  name  varies.  See  also  the  footnotes 
which  Professor  A.  Sanroma  Nicolau  added  to  his  excellent  translation  of  "Discovery 
of  the  Elements"  ( 24  ) . 


CONTRIBUTIONS  OF  THE  DE  ELHXJYAR  BROTHERS  287 


From  F.  G.  Corning,  "A  Student  Reverie" 


Abraham  Gottlob  Werner,  1750-1817.  Professor  of  geog 
nosy  at  the  Freiberg  School  of  Mines.  Because  his  fol 
lowers  believed  in  the  aqueous  origin  of  rocks,  they  were 
called  Neptunists.  Among  his  distinguished  students  were 
the  de  Elhuyar  brothers,  Baron  Alexander  von  Humboldt, 
and  A.  M.  del  Rio,  the  discoverer  of  vanadium  (eryth- 
roniurn ) . 


When  Don  Fausto  took  up  his  teaching  duties  at  Vergara  just  after 
the  Christmas  vacation  in  1781,*  he  was  already  famous  because  of  his 
achievements  in  northern  Europe.  He  soon  published  papers  on  the 
manufacture  of  tin  plate,  the  mines  of  Somorrostro,  the  ironworks  of 
Biscaya,  and  the  working  of  copper  mines. 

Soon  after  devoting  themselves  to  laboratory  research  in  Vergara, 
the  de  Elhuyar  brothers  analyzed  a  specimen  of  wolframite  from  a  tin 
mine  in  Zmnwald  and  separated  from  it  an  insoluble  yellow  powder 

*  The  author  wishes  to  correct  a  statement  in  Reference  8.    Elhnyar  taught  at  Vergara 
before  going  to  Mexico,  not  after  his  return. 


288  DISCOVERY  OF  THE  ELEMENTS 

which  they  called  wolframic  acid  and  which  they  later  showed  to  be 
identical  with  tungstic  acid.  Since  these  Spanish  chemists  were  the 
first  to  reduce  wolframic  acid,  Dr.  E.  Moles  of  the  University  of  Madrid 
and  Dr.  Fages  y  Virgili  pointed  out  that  the  metal  ought  to  be  called 
by  the  name  wolframium  (wolfram)  which  the  de  Elhuyar  brothers  gave 
it.  Although  this  name  (4}  has  been  changed  in  some  languages  to 
forms  derived  from  tungstein,  the  accepted  international  symbol,  W,  still 
bears  witness  that  the  metal  was  first  obtained  from  wolframite,  not 
from  tungstein  (scheelite). 

Although  the  isolation  of  this  metal  has  sometimes  been  erroneously 
credited  to  Don  Fausto  alone,  the  original  paper  published  in  1783  in 
the  Extractos  de  las  Juntas  Generates  of  the  Royal  Basque  Society  under 
the  title  "Chemical  Analysis  of  Wolfram  and  Examination  of  a  new  Metal 
which  Enters  into  its  Composition"  bore  the  names  of  both  brothers. 
Because  of  the  great  importance  of  this  memoir  it  was  soon  translated  into 
French,  English,  and  German  (5). 

Dr.  Fages  and  Dr.  Moles  both  pointed  out  that,  in  isolating  the  new 
metal,  the  de  Elhuyar  brothers  did  much  more  than  merely  confirm  the 
hypothesis  of  Torbern  Bergman.  Instead  of  analyzing  tungstic  acid  in 
tentionally  prepared  to  test  this  hypothesis,  as  has  so  often  been  stated, 
they  analyzed  wolfram  without  any  preconceived  ideas.  Dr.  Fages  stated 
that,  after  the  de  Elhuyar  brothers  had  discovered  the  acid  in  wolframite: 

.  .  .  their  great  enlightenment  and  erudition,  supporting  their  great  genius, 
caused  them  to  suppose  that  the  earth  encountered,  completely  new  to  them 
and  to  almost  all  chemists,  might  be  the  same  that  Scheele  had  discovered  a  few 
months  before  in  another  mineral,  entirely  independently  .  .  .  (4,6). 

The  de  Elhuyar  brothers  concluded  from  their  analysis  that  wolf 
ramite  is  composed  of  wolframic  acid  combined  with  iron  and  manganese. 
Their  method  of  obtaining  the  metal  by  reduction  of  tungstic  (wolframic) 
acid  with  charcoal  has  been  described  in  other  papers  (4,  6,  7,  8).  As 
late  as  1786  the  great  analytical  chemist  Martin  Heinrich  Klaproth  ad 
mitted  that  all  his  own  attempts  had  failed  and  that  "up  to  the  present 
only  Hr.  Elhuyar  has  succeeded  in  getting  the  metal"  ( 9 ) . 

Although  the  de  Elhuyar  brothers  were  unsuccessful  in  their  attempts 
to  synthesize  wolframite,  they  foreshadowed  modern  methods  of  mineral 
synthesis  (3).  They  also  devised  an  ingenious  method  of  determining 
the  specific  gravity  of  solids,  and  their  values  for  wolframite,  tungsten 
trioxide,  and  metallic  tungsten  were  surprisingly  accurate  (2).  Their 
dissertation  on  wolframite,  published  three-quarters  of  a  century  before 
Thomas  Graham  founded  the  science  of  colloid  chemistry,  contains  a 
clear  description  of  a  wolframic  (tungstic)  acid  sol  (2).  Spanish  writers 
have  commented  on  the  lucid  and  refined  style  of  this  great  memoir. 


CONTRIBUTIONS  OF  THE  DE  ELHUYAR  BROTHERS  289 

which,  though  written  in  the  phraseology  of  the  phlogistonists,  exhibits 
scientific  concepts  and  technic  which  are  astonishingly  modern.  In  the 
French  translation  of  it,  the  de  Elhuyar  brothers  modestly  admit  that 
no  use  has  yet  been  found  for  the  new  metal,  but  add  that  "we  must 
not  conclude  from  this  that  it  is  entirely  useless"  (3). 

In  the  meantime,  events  in  the  western  hemisphere  had  caused  King 
Charles  to  make  new  plans  for  the  de  Elhuyar  brothers.  As  early  as 
1774  Don  Joaquin  de  Velazquez  Cardenas  y  Leon  had  presented  a  plan 
for  the  establishment  of  a  school  of  mines  at  Mexico  City  which  had 
received  the  King's  approval.  However,  the  realization  of  the  plan  had 
unfortunately  been  deferred  by  the  death  in  1786  of  this  distinguished 
Mexican  scientist.  In  order  to  fulfill  his  cherished  hope  of  developing  the 
mines  of  America,  King  Charles  sent  Don  Juan  Jose  to  New  Granada 
( Colombia )  and  Don  Fausto  to  Hungary  and  Germany  to  prepare  him 
self  for  the  exacting  duties  of  Director  General  of  Mines  of  Mexico  (2,  6). 

The  former  served  for  many  years  as  professor  of  mineralogy,  suc 
cessfully  administered  technical  commissions  of  great  responsibility,  and 
developed  the  mines  of  New  Granada.  Early  in  the  spring  of  1786  Don 
Fausto  collaborated  with  Frangois  Chabaneau,  professor  of  chemistry 
at  Vergara,  in  some  remarkable  researches  on  platinum.  In  a  letter  written 
in  Vergara  on  March  17th  of  that  year  to  Don  Juan  Jose",  who  was  then 
living  in  Bogota,  Colombia,  Don  Fausto  gave  a  clear  description  of  their 
process  for  making  pure  platinum  malleable.  In  his  bibliography  of 
Spanish  science,  Menendez  y  Pelayo  mentions  a  paper  on  locating  veins 
of  mercury  which  Don  Juan  Jose  published  in  the  same  year  (10). 

Don  Juan  Jose  was  a  highly  esteemed  friend  of  the  great  Spanish 
botanist,  Don  Jose  Celestino  Mutis,  who  once  said  proudly,  "I  have  been 
the  instrument  for  the  glorious  acquiring  of  the  two  learned  D'Elhuyar 
[sic]  brothers  and  the  rapid  introduction  of  Baron  Bora's  new  mining 
process"  (11).  In  1932  the  Republic  of  Colombia  celebrated  the  bi 
centenary  of  the  birth  of  this  great  Spanish  botanist  ( 12 ) .  According  to 
Dr.  Fages,  many  documents  preserved  with  the  famous  Mutis  collection 
at  the  Botanical  Garden  in  Madrid  show  that  the  services  of  Don  Juan 
Jose  in  New  Granada  were  no  less  useful  to  Spain  that  those  of  his 
younger  brother  in  Mexico.  Don  Juan  Jose  de  Elhuyar  died  on  Septem 
ber  20,  1796,  in  the  Santa  Ana  mine  at  Bogota,  without  ever  revisiting 
his  native  land  (6,  II). 

Don  Juan  Fages  y  Virgili  stated  long  ago  that  many  Spanish  writers 
had  wrongly  attributed  the  discovery  of  tungsten  (wolfram)  solely  to 
Don  Fausto  whereas  foreign  writers  gave  the  credit  to  both  brothers. 
"As  for  me,"  he  continued,  "I  find  no  fact  which  would  make  me  assume 
that  Don  Fausto  was  the  competent  and  brilliant  one  and  that  Don 
Juan  Jose  played  only  a  secondary  part.  Perhaps  a  thorough  examina- 


290  DISCOVERY  OF  THE  ELEMENTS 

tion  would  lead  one  to  think  not  just  the  opposite,  but  that  in  the  work 
on  wolfram  Don  Juan  Jose  played  a  larger  part  than  did  Don  Fausto" 
(25).  This  too  is  the  opinion  expressed  by  Dr.  Stig  Ryden  of  the  Ibero- 
American  Institute  of  Gothenburg,  Sweden,  in  his  excellent  booklet  "Don 
Juan  Jose  de  Elhuyar  in  Sweden  (1781-1782)  and  the  discovery  of 
tungsten,"  which  was  published  in  1954  in  honor  of  the  bicentenary  of 
the  birth  of  Don  Juan  Jose  (26).  Although  it  was  difficult  to  decide 
from  the  early  literature  which  of  the  brothers  studied  in  Sweden,  Dr. 
Arthur  P.  Whitaker  (27)  and  Dr.  Stig  Ryden  (26,  28)  have  proved  con 
vincingly  that  Don  Juan  Jose  (not  Don  Fausto)  studied  there  under 
Torbern  Bergman  in  1781-82.  Much  of  the  confusion  that  previously 
existed  was  caused  by  Don  Juan  Jose's  habit  of  signing  his  name  merely 
as  "de  Luyarte  EspagnoF  (de  Luyarte  Spaniard).  The  fact  that  the 
two  brothers  did  not  agree  on  the  spelling  of  the  surname  is  mentioned 
on  page  255  of  this  book.  By  correspondence  with  a  descendant  of 
Don  Juan  Jose,  Mr.  Bernardo  J.  Caycedo  of  Bogota,  Dr.  Ryden  learned 
that  Don  Juan  Jose  died  on  September  20,  1796  (not  in  1804),  and  that 
he  preferred  the  name  tungsten  which  Bergman  gave  to  the  new  metal 
rather  than  wolfram.  Mr.  Caycedo  is  writing  a  biography  of  his  dis 
tinguished  ancestor. 

On  May  22,  1783,  while  the  de  Elhuyar  brothers  were  still  en 
grossed  in  their  famous  experiments  on  wolframite,  the  King  had  issued 
his  "Royal  Ordinances  for  the  Direction,  Management,  and  Government 
of  the  Important  Body  of  Mining  in  New  Spain  and  of  its  Royal  General 
Tribunal  (13)"  In  the  spring  of  1786  Don  Fausto  de  Elhuyar  was  sent 
to  Hungary  and  Germany  to  study  the  new  method  of  amalgamation 
which  Counselor  Born  had  established  in  Schemnitz  and  Freiberg.  Be 
cause  of  Born's  useful  discovery  of  a  method  of  extracting  noble  metals 
from  ores  by  means  of  mercury  and  of  separating  the  silver  from  the 
mercury  by  pressing  the  latter  through  leather  the  Austrian  poet  Aloy's 
Blumauer  dedicated  the  following  poem*  to  him: 

Die  Schatze,  die  bisher  nur  allzutheuer 

Sich  die  Natur  von  uns  bezahlen  liess, 

Und  die  der  Mensch  ihr  nur  durch  Gift  und  Feuer 

Und  durch  Gewalt  mit  Idhmer  Hand  entriss, 

Die  schenkt  sie  dir—zum  sichern  Unterpfand, 

Doss  du  ihr  Liebling  bist—auf  einen  Druck  der  Hand  (23)* 
*  The  following  is  an  approximate  prose  translation: 

Treasures  which  Nature  hitherto 

Has  yielded  but  too  dearly, 

And  which  mankind  from  her  has  snatched 

Only  with  risk  through  poison,  fire,  and  force, 

On  you  she  doth  bestow— as  certain  pledge 

That  you  her  minion  are— 

At  a  pressure  of  the  hand. 


CONTRIBUTIONS  OF  THE  DE  ELHUYAR  BROTHERS     291 

On  July  18,  1786,  the  Marquis  of  Sonora  wrote  as  follows  to  Don 
Fausto,  who  was  then  in  Vienna: 

The  King  has  deigned  to  appoint  Your  Excellency  as  Director  General  of 
the  Royal  Assembly  of  Mines  of  Mexico  with  a  salary  of  4000  pesos,  and  by  his 
Royal  command  I  give  you  this  order  for  your  satisfaction,  and  that,  well  in 
formed  on  the  new  method  of  amalgamation  that  Mr.  Born  invented,  you  may 
return  to  those  realms  at  your  earliest  convenience  in  order  to  go  to  New  Spain 
and  fill  that  office  with  the  intelligence  and  knowledge  which  the  discharge  of 
your  obligation  demands  and  which  His  Majesty  expects  from  your  application, 
proficiency,  and  zeal  (13). 

After  a  year  and  a  half  in  Hungary  and  Germany,  Professor  Elhuyar 
spent  a  few  months  in  Vienna  studying  the  mines  of  the  surrounding 
region  and  the  metallurgy  of  many  metals  and  enjoying  the  brilliant 
social  life  of  the  city.  Before  returning  to  Spain  he  married  a  German 
lady  of  distinguished  lineage,  Juana  Raab  de  Moncelos,  who,  in  the  middle 
of  June,  1788,  set  sail  with  him  from  Cadiz  for  New  Spain  (11,  21}. 

When  the  frigate  Venus  cast  anchor  at  Vera  Cruz  on  September  4th 
of  that  year,  the  new  Director  General  of  Mines  disembarked  and  went 
immediately  to  Mexico  City.  After  a  solemn  and  colorful  ceremony 
in  the  Royal  Palace,  he  entered  at  once  into  his  new  duties. 

A  few  months  later,  as  a  first  step  in  the  construction  of  a  chemical 
laboratory,  assay  furnaces  were  built  in  the  patio  of  the  college  building. 
According  to  Director  Elhuyar's  plan,  the  students  admitted  were  to 
range  in  age  from  fifteen  to  twenty  years  and  were  to  wear  a  prescribed 
blue  uniform  with  red  collar  and  cuffs  and  gold  buttons  decorated  with 
the  signs  for  gold,  silver,  and  mercury.  On  Sundays  and  church  holi 
days  they  were  expected  to  attend  the  church  functions,  both  morning 
and  afternoon,  and  to  call  on  the  mining  officials  "in  order  to  learn  the 
usages  of  polite  society  (13}!'  As  an  incentive  to  scholarship,  the  Director 
arranged  that  prizes  for  good  conduct  and  industry  should  be  awarded 
with  great  solemnity.  These  consisted  of  ornaments  to  be  worn  in  the 
buttonhole  (13).  The  School  of  Mines  was  officially  opened  on  New 
Year's  Day,  1792,  with  an  impressive  ceremony  in  the  Church  of  San 
Nicolas.  It  was  the  first  scientific  institution  to  be  erected  on  Mexican 
soil  (14}. 

The  researches  which  Don  Fausto  had  already  carried  out  at  Freiberg 
on  Bern's  amalgamation  process  are  discussed  in  Professor  Modesto  Bar- 
gallo's  recent  book  on  mining  and  metallurgy  in  Colonial  Spanish  Amer 
ica  (29).  The  original  publication  on  these  researches  appeared  in  Spain 
in  1791,  three  years  after  Don  Fausto's  arrival  in  Mexico.  L.-J.  Proust,  who 
was  then  teaching  in  the  Academy  of  Artillery  at  Segovia,  reviewed  these 


292  DISCOVERY  OF  THE  ELEMENTS 


Don  Andres  Manuel  del  Rio,*  1764-1849.  Professor  of 
mineralogy,  French,  and  Spanish  at  the  School  of  Mines 
of  Mexico.  Member  of  the  American  Philosophical  So 
ciety.  He  discovered  the  element  vanadium  (erythro- 
nium ) ,  bxit  later  confused  it  with  chromium.  This  portrait 
belongs  to  the  school  of  mines  of  Mexico. 


*  The  author  wishes  to  thank  Senor  Pablo  Martinez  del  Rio,  head  of  the  Extension 
Dept.  of  the  National  University  of  Mexico?  for  his  kind  assistance  in  locating  this 
portrait. 


CONTRIBUTIONS  OF  THE  DE  ELHUYAR  BROTHERS 


293 


remarkable  experiments  of  Elhuyar  in  volume  one  of  the  Andes  del  Real 
Laboratorio  de  Quimica  in  1791.  The  late  Senor  J.  R.  Mourelo  once 
stated  that  ".  .  .  the  glory  of  both  [Bartolome  de  Medina  and  Alvaro 
Alonso  Barba]  shines  and  scintillates  more  brightly  in  that  of  ...  the 
famous  mining  engineer,  Don  Fausto  Elhuyar,  in  whom  appears  com 
pleted  ...  the  magnificent  work  of  those  eminent  miners  .  .  "  (15). 


Courtesy  F.  B.  Dains 

Baron  Alexander  von  Humboldt,   1769-1859.      German 
naturalist  and  traveler.    Author  of  "Kosmos"  and  "Politi 
cal  Essay  on  New  Spain."    Friend  of  Fausto  de  Elhuyar 
and  A.  M.  del  Rio.    See  also  ref.  (30). 

Since  a  royal  order,  transmitted  through  the  Viceroy  of  Mexico,  had 
decreed  that  Werner's  theory  of  the  formation  of  veins  be  taught  to 
the  students,  the  brilliant  young  Don  Andres  Manuel  del  Rio  was  sent  to 
Mexico  to  introduce  the  most  approved  mining  methods  which  he  had 
learned  at  Freiberg  (13).  Although  del  Rio  had  declined  the  pro 
fessorship  of  chemistry,  he  accepted  that  of  mineralogy,  and  took  with 
him  on  the  warship  San  Pedro  Alcantara  a  quantity  of  equipment  for  the 
School  of  Mines.  Soon  after  his  arrival  in  Mexico  City  in  December,  1794, 


294  DISCOVERY  OF  THE  ELEMENTS 

Don  Fausto  de  Elhuyar  asked  him  to  translate  Werner's  book  on  the 
theory  of  formation  of  veins  into  Spanish  (13}. 

When  Senor  Elhuyar  s  nine-year  term  as  Director  was  about  to  ex 
pire  in  1797?  his  colleagues  and  students  requested  that  he  be  reappointed 
for  another  nine  years,  or  for  life,  or  for  whatever  period  might  meet 
with  Royal  favor  (13).  The  report  stated  that  ".  .  .  this  Royal  Seminary 
is  persuaded  that  in  this  kingdom  there  is  no  other  subject  of  the  merit 
and  circumstances  so  suited  to  this  institution  ...  as  Sr.  D.  Fausto  Eluyar 
[sic]"  The  officers  of  the  school  felt  that  no  one  else  "would  recognize 
the  character  and  genius  of  the  [Mexican]  people/'  The  association  of 
mining  engineers  from  all  parts  of  Mexico  also  voted  unanimously  for 
his  reappointment,  and  the  request  was  granted  (13). 

In  the  meantime  Don  Fausto  made  many  inspection  trips  to  mining 
centers,  supervised  the  installation  of  pumps  of  his  own  invention,  and 
for  several  months  taught  the  chemistry  course,  because  of  the  illness  of 
Don  Luis  Lindner.  Under  his  leadership  the  prestige  of  the  school  in 
creased,  and  students  came  from  distant  parts  of  Mexico  to  obtain  a 
broad  cultural  foundation  as  well  as  a  practical  knowledge  of  mining. 
In  April,  1798,  the  King  ordered  that  some  of  the  most  promising  youths 
be  selected  by  examination  to  become  directors  and  mining  engineers  in 
the  viceroyships  of  Peru  and  Buenos  Aires  and  the  provinces  of  Quito, 
Guatemala,  and  Chile,  and  to  establish  safe,  economical  methods  for  the 
exploitation  of  the  precious  metals  (13). 

After  Baron  Alexander  von  Humboldt  had  visited  Mexico  in  1803, 
he  wrote  that  "no  city  of  the  new  continent,  without  excepting  those  of 
the  United  States,  presents  scientific  establishments  so  large  and  sub 
stantial  as  the  Capital  of  Mexico.  I  shall  mention  ...  the  School  of 
Mines,  directed  by  the  learned  Elhuyar  .  .  ."  (16). 

The  Baron  also  stated  that 

...  a  European  traveler  would  be  surprised  to  meet  in  the  interior  of  the 
country,  near  the  California  boundary,  young  Mexicans  reasoning  on  the  de 
composition  of  water  in  the  operation  of  amalgamation  in  the  open  air.  The 
School  of  Mines  has  a  chemical  laboratory,  a  geological  collection  classified  ac 
cording  to  Werner's  system,  and  a  physical  laboratory,  in  which  are  to  be  found 
not  only  valuable  instruments  of  Ramsden,  Adams,  Lenoir,  and  Luis  Berthoud, 
but  also  models  made  in  the  same  capital  with  the  greatest  precision  and  of  the 
best  wood  in  the  country.  The  best  mineralogical  work  which  Spanish  literature 
possesses,  the  manual  of  mineralogy  arranged  by  Senor  del  Rio  according  to 
the  principles  of  the  Freiberg  School,  where  the  author  studied,  has  been 
printed  in  Mexico  (16) . 

The  Baron  also  mentioned  A.-L.  Lavoisier's  "Elements  of  Chem 
istry,"  the  first  Spanish  edition  of  which  was  published  in  Mexico.  J.-A.-C. 


CONTRIBUTIONS  OF  THE  DE  ELHUYAB  BROTHERS 


295 


A  LA  ESCLARECIDA  MEMORIA 


J*r.m«  Ptnwmr  Ocnand  do  Stuwrf* 


D.  FAUSTO  DE  ELHUYAR 


DEL  GOLEGIO  DE  MINEEf  A 


En  Ustimonio  d«  car!5or  ds  admlracion  y  gratitud, 


Dedication  of  the  History  of  the  College  of  Mines  of 

Mexico  (Ref.  13).  Translation:  "To  the  illustrious 
memory  of  the  eminent  scientists  who  filled  with  excep 
tional  ability  the  important  office  of  First  Director  Gen 
eral  of  Mining,  D.  Joaquin  de  Velazquez  Cardenas  y 
Leon  and  D.  Fausto  de  Elhuyar,  the  former  the  initiator 
and  the  latter  the  founder  of  the  College  of  Mines.  In 
testimony  of  affection,  admiration,  and  gratitude." 

ChaptaFs  textbook  of  chemistry  was  also  used  at  the  Mining  Academy, 
but  in  1820  it  was  superseded  by  that  of  M.-J.-B.  Orfila  (13). 

Professor  Elhuyar  often  ordered  instruments  for  the  School  of  Mines 
through  von  Humboldt,  who  selected  and  purchased  them  without  any 
commission.  In  return  for  this  courtesy  he  gave  the  Baron  much  valuable 
information  for  his  "Political  Essay  on  New  Spain"  (13,  16).  Von  Hum 
boldt  later  presented  to  European  museums  numerous  specimens  of 
Mexican  minerals  which  this  Spanish  scientist  had  given  him. 


296  DISCOVERY  OF  THE  ELEMENTS 


CONTRIBUTIONS  OF  THE  DE  ELHUYAR  BROTHERS  297 

Two  of  de  Elhuyar's  most  famous  papers  were  entitled  "Suggestions 
on  Coining  in  New  Spain"  and  "Memoir  on  the  Influence  of  Mining  on 
the  Agriculture,  Industry,  Population,  and  Civilization  of  New  Spain" 
(17,  18).  In  his  "History  of  Mexico"  (19),  H.  H.  Bancroft  extolled  the 
former  treatise  as  follows: 

With  regard  to  the  mint  and  coinage  I  find  the  work  of  Fausto  de  Elhuyar, 
entitled  Indigaciones  sobre  la  Amonedacion  en  la  Nueva  Espana,  Madrid,  1818, 
to  be  extremely  useful.  His  researches  were  conducted  with  great  care,  and 
supply  a  concise  and  correct  history  of  the  mint  from  its  establishment  down  to 
the  10th  of  August,  1814,  when  he  laid  before  the  mining  tribunal  of  Mexico,  of 
which  he  was  director,  the  results  of  his  labors.  In  this  book,  which  consists  of 
142  pages,  he  gives  an  account  of  the  different  coins  struck  off  and  the  modifica 
tions  which  they  experienced  at  different  periods,  also  of  the  new  system  when 
the  administration  was  assumed  by  the  government.  He  moreover  considers 
with  attention  the  causes  by  which  the  interests  of  the  mining  industry  suffered, 
and  suggests  remedies. 

During  the  war  of  independence,  the  once  prosperous  mining  in 
dustry  of  Mexico  passed  through  such  a  serious  depression  that  all  courses 
at  the  School  of  Mines  were  suspended,  with  humane  provision,  however, 
for  those  of  its  employees  who  had  no  other  source  of  income.  Don 
Fausto  de  Elhuyar  relinquished  his  authority,  and  thus,  after  thirty- 
three  years  of  service,  his  directorship  came  to  a  close  on  October  22, 
1821.  The  history  of  the  School  of  Mines  (13)  by  the  distinguished 
mining  engineer,  Santiago  Ramirez,  contains  a  wealth  of  information 
about  Elhuyar's  services  to  Mexico. 

After  returning  to  Madrid,  Professor  Elhuyar  was  made  a  member 
of  the  General  Council  of  Public  Credit  (13),  served  on  many  govern 
ment  commissions,  wrote  his  famous  treatise  on  the  influence  of  mining 
in  New  Spain  (17),  drew  up  the  new  mining  law  known  as  the  Royal 
Decree  of  July  4,  1825,  and  was  made  Director  General  of  Mining**  (20, 
22).  He  planned  the  School  of  Mining  Engineering  of  Madrid  and 
organized  and  developed  the  mining  industry  of  his  native  land,  which 
he  served  devotedly  to  the  end  of  his  life.  One  of  the  reforms  which  he 
advocated  was  the  eight-hour  day  (2). 

In  spite  of  his  many  positions  of  influence  and  responsibility,  Pro 
fessor  Elhuyar  lived  in  modest  circumstances,  devoting  all  his  energy 
to  intellectual  rather  than  material  pursuits.  He  died  at  Madrid  on 
January  6,  1833,  at  the  age  of  seventy-seven  years.  Although  the  cen 
tenary  of  Elhuyar's  death  was  observed  on  February  6,  1933,  the  death 
certificate  which  Sefior  de  Galvez-Canero  discovered  in  the  records  of 

*  Although  standard  Spanish  and  German  encyclopedias  state  that  Don  Fausto  de 
Elhuyar  also  became  Secretary  of  State,  Dr.  Fages  (6)  pointed  out  that  this  is  incorrect. 


298 


DISCOVERY  OF  THE  ELEMENTS 


San  Sebastian  parish  in  Madrid  states  that  Don  Fausto  died  on  January 
6th  as  the  result  o£  a  fall  (II). 

In  1892  the  Mexican  government  under  Porfirio  Diaz,  the  former 
students  of  the  Mining  Academy,  and  the  leading  mining  companies 
arranged  a  mining  exposition  and  a  series  of  public  functions  throughout 


Courtesy  Dr.  Moles  and  Mr.  de  Gdlvez-Canero 


Fausto  de  Elhuyar,  Director  General  of  Mines  of  Spain. 

The  centenary  of  his  death  was  observed  in  1933  at 

the  School  of  Mining  Engineering  of  Madrid. 


the  year  to  commemorate  the  centennial  anniversary  of  the  founding  of 
the  Seminary.  All  the  scientific  organizations  in  the  country  partici 
pated,  and  the  German  musical  society,  the  Orfeon  Alemdn,  gladly  co 
operated  out  of  gratitude  for  the  honors  which  the  Seminary  had  bestowed 
on  Baron  von  Humboldt  In  each  arch  of  the  magnificent  college  build* 
ing  appeared  a  flag-draped  escutcheon  bearing  an  honored  name,  and 


CONTRIBUTIONS  OF  THE  DE  ELHUYAR  BROTHERS  299 

foremost  among  these  were  Joaquin  de  Velazquez  Cardenas  y  Leon, 
Fausto  de  Elhuyar,  and  Andres  Manuel  del  Rio  (14). 

On  February  6,  1933,  the  Spanish  Society  of  Physics  and  Chemistry, 
the  Geological  and  Mining  Institute  of  Spain,  and  the  Association  of 
Mining  Engineers  met  at  the  School  of  Mining  Engineering  of  Madrid 
to  observe  the  one-hundredth  anniversary  of  the  death  of  Don  Fausto  de 
Elhuyar.  Eloquent  and  scholarly  addresses  on  the  various  phases  of  his 
services  to  science  were  delivered  by  Sefiores  Bermejo,  Hauser,  Galvez- 
Cafiero,  Enrique  Moles,  Novo,  and  Lopez  Sanchez  Avecilla,  and  three 
portraits*  of  him  were  displayed  by  Senor  de  Galvez-Canero,  who  pub 
lished  in  1933  a  beautifully  illustrated  biography  based  on  authentic 
documents  and  correspondence.  Plans  were  announced  for  the  publica 
tion  of  some  of  Don  Fausto's  papers  in  a  series  of  Spanish  scientific 
classics,  and  the  Elhuyar  Prize  of  1000  pesetas  was  awarded  to  Don 
Fernando  Gonzalez  Nunez  for  his  revision  of  the  atomic  weight  of 
chromium  (2). 

Acknowledgment 

The  writer  is  deeply  grateful  to  Professor  E.  Moles,  Mr.  A.  de  Galvez- 
Caiiero  y  Alzola,  Dr.  F.  G.  Corning,  Senor  Pablo  Martinez  del  Rio,  and 
Dr.  F.  B.  Dains  for  the  use  of  the  illustrations  accompanying  this  chapter. 
It  is  also  a  pleasure  to  acknowledge  the  valuable  help  obtained  from  the 
literature  on  the  history  of  Spanish  chemistry  which  Dr.  Moles,  Mr.  de 
Galvez-Canero,  Dr.  Stig  Ryden,  Mr.  Bernardo  J.  Caycedo,  and  Professor 
Modesto  Bargallo  so  kindly  contributed. 


LITERATURE  CITED 

( 1 )  SEMPERE,  J.,  "Ensayo  de  una  biblioteca  espanola  de  los  mejores  escritores  del 

Reynado  de  Carlos  III,"  Imprenta  Real  Madrid,  1789,  Vol.  5,  pp.  151-77. 

(2)  "El  primer  centenario  de  D.  Fausto  de  Elhuyar,"  Anales  soc.  espan.  fis  quim., 

31,115-43  (Mar.  15,1933). 

(3)  Ateneo  cientifico,  literario,  y  artistico  de  Madrid,  "La  Espana  del  Siglo  XIX," 

Libreria  de  D.  Antonio  San  Martin,  Madrid,  1886,  Vol.  2,  pp.  412^-52. 
Chapter  on  the  history  of  the  physical  sciences  by  Mourelo. 

(4)  MOLES,   E.,   "Wolframio,   no  tungsteno.     Vanadio    o   eritronio,"   Anales  soc. 

espan.  fis.  quim.,  [3],  26,  234-52  (June,  1928). 

(5)  ELHUYAR,  J.  J.  and  F.,  "Analisis  quimico,de  volfram  y  examen  de  un  nuevo 

metal  que  entra  en  su  composicion,"  Extractos  Real  Soc.  Bascongada,  1783, 
pp.  46-88;  Memoires  Acad.  Toulouse,  2,  141-68  (1784);  English  translation 
by  CHARLES  CULLEN,  G.  Nicol,  London,  1785;  German  translation  by  F.  A. 
C.  GREN,  Halle,  1786. 

*  Senor  Bermejo,  president  of  the  Spanish  Society  of  Physics  and  Chemistry,  also 
mentioned  that  there  is  a  statue  of  Fausto  de  Elhuyar  at  the  Faculty  of  Sciences  of 
Saragossa. 


300  DISCOVERY  OF  THE  ELEMENTS 

(6)  "Discursos  leidos  ante  la  Real  Academia  de  Ciencias  en  la  recepcion  publica 

del  Ilmo,  Sr.  D.  Juan  Pages  y  Virgili,"  Madrid,  1909,  118  pp.  Address  on 
"The  chemists  of  Vergara." 

(7)  KOPPEL,  L,  "Beitrag  zur  Entdeckungsgeschichte  des  Wolframs,"  Chem.-Ztg., 

50,  969-71  (Dec.  25,  1926). 

(8)  WEEKS,  M.  E.,  "The  discovery  of  the  elements.    V.    Chromium,  molybdenum, 

tungsten,  and  uranium/'  J.  Chem.  Educ.,  9,  459-61  (Mar.,  1932);  ibid., 
Mack  Printing  Co.,  Easton,  Pa.,  1933,  pp.  50-2. 

(9)  KLAPROTH,    M.    H.,    "Untersuchung    des    angeblichen    Tungsteins    und    des 

Wolframs  aus  Cornwall,"  Crell's  Ann.,  6,  507  ( 1786). 

(10)  MENENDEZ,   M.,  "La  ciencia  espafiola,"  3rd  ed.,  Vol.  3,  A.   Perez  Dubruli, 

Madrid,  1888,  pp.  395-6. 

(11)  DE  GALVEZ-CANERO,  A.,  "Apuntes  biograficos  de  D.  Fausto  de  Elhuyar  y  de 

Zubice,"  Boletin  del  Institute  Geologico  y  Miner o  de  Espana,  Vol.  53,  Graficas 
reunidas,  Madrid,  1933,  253  pp. 

(12)  Anuario  Acad.  Ciencias,  Madrid,  pp.  180-1   (1932);  "Century-old  collection 

yields  new  plant  species,"  Sci.  News  Letter,  24,  135  (Aug.  26,  1933). 

(13)  RAMIREZ,  S.,  "Datos  para  la  historia  del  Colegio  de  Mineria,"  Government 

publication  for  the  Sociedad  cientifica  Antonio  Alzate,  Mexico  City,  1890, 
494  pp. 

(14)  RAMIREZ,   S.,   "El   centenario   del  Colegio   de   Mineria,"   Sociedad   cientifica 

Antonio  Alzate,  Memorias  y  revista,  6,  177-242  ( 1892-93 ) . 

(15)  MOURELO,  J.  R.,  "Un  libro  famoso,"  Revista  acad.  ciencias  (Madrid),  29,  9-52 

(Sept.,  1932).    Review  of  BARBA,  A.  A.,  "El  Arte  de  los  Metales,"  1640. 

(16)  HUMBOLDT,    A.,    "Ensayo    politico    sobre    Nueva   Espana,"    3rd    ed.,    Vol.    1, 

Libreria  de  Lecointe,  Paris,  1836,  pp.  232,  236-8;  ibid.,  Vol.  2,  p.  85;  C.  A. 
BROWNE,  "Alexander  von  Humboldt  in  some  of  his  relations  to  chemistry," 
J.  Chem.  Educ.,  21,  211-15  (May,  1944). 

(17)  ELHUYAR,  F.,  "Indigaciones  sobre  la  amonedacion  en  Nueva  Espana,"  Imprenta 

de  la  calle  de  la  Greda,  Madrid,  1818,  146  pp.;  "Memoria  sobre  el  influjo  de 
la  minena  en  la  agricultura,  industria,  poblacion,  y  civilizacion  de  la  Nueva 
Espana,"  Imprenta  de  Amarita,  Madrid,  1825,  154  pp. 

(18)  RAMIREZ,  S.,  "Noticia  historica  de  la  riqueza  minera  de  Mexico,"  Secretaria  de 

Fomento,  Mexico,  1884,  768  pp. 

(19)  "The  Works  of  Hubert  Howe  Bancroft,"  Vol.  11,  A.  L.  Bancroft  and  Co.,  San 

Francisco,  1883,  p.  679. 

(20)  MOROS,   F.   A.,    "Minerals   y   mineralogistas    espanoles,"   Revista   Real   acad. 

ciencias  (Madrid),  21,  299  (1923-24). 

(21)  ARNAIZ  Y  FREG,  ARTURO,  "D.  Fausto  de  Elhuyar  y  de  Zubice,"  Revista  de 

Historia  de  America  (Mexico),  No.  6,  75-96  (Aug.,  1939). 

(22)  WHTTAKER,  A.  P.,  "More  about  Fausto  de  Elhuyar,"  Revista  de  Historia  de 

America  (Mexico),  No.  10,  125-30  (Dec.,  1940). 

(23)  "Gedichte  von  Aloy's  Blumauer,"  part  1,  Salomo  Lincke,  Leipzig,  1801,  p.  53. 
( 24  )     WEEKS,  M.  E.,  "Historia  de  los  Elementos  Quimicos,"  Manuel  Marin,  Barcelona, 

1949,  pp.  132,  133,  144.    Translated  by  A.  Sanroma  Nicolau. 

(25)  "Discursos   leidos   ante   la   Real  Academia    de    Ciencias   Exaotas,    Fisicas    y 

Naturales  en  la  recepcion  publica  del  Ilmo.  Sr.  D.  Juan  Fages  y  Virgili  el 
dia  27  de  Junio  de  1909,"  Establecimiento  Tipografico  y  Editorial  Pontelos 
Madrid,  1909,  p.  92. 

(26)  RYDEN,  STIG,  "Don  Juan  Jose  de  Elhuyar  en  Suecia  (1781-1782)  y  el  descub- 

rimiento  del  tungsteno,"  Insula,  Madrid,  1954,  69  pp. 


CONTRIBUTIONS  OF  THE  DE  ELHUYAR  BROTHERS  301 

(27)  WHITAKER,  ARTHUR  P.  "Las  misiones  mineras  de  los  Elhuyar  y  la  Ilustracion," 

Revista  Chilena  de  Historia  y  Geografia,  Santiago  de  Chile,  No.  120,  pp. 
136-7  (1952);  The  Hispanic  American  Historical  Review,  31,  4  (1951). 
Cited  in  ref.  (26). 

(28)  RYDEN,  STIG,  "Kungliga  Baskiska  Sallskapet  av  Vanner  till  Hembygden,"  Re 

print  from  Med  Hammare  och  Fackla,  XX,  1-74  (1953-54) 

(29)  BARGALLO,  MODESTO,  "La  mineria  y  la  metalurgia  en  la  America  Espanola 

durante  la  epoca  colonial,"  Fondo  de  Cultura  Economica,  Mexico  City  and 
Buenos  Aires,  1955,  442  pp. 

(30)  BITTERLING,  RICHARD,  ALEXANDER  VON  HUMBOLT,   "Deutscher  Kunstverlag," 

Munich  and  Berlin,  1959,  116  pp. 


Jons  Jacob  Berzelius,  1779-1848.  Professor  of  chemistry  and  medicine  at 
the  Stockholm  Medical  School.  He  determined  the  atomic  weights  of  most 
of  the  elements  then  known,  discovered  selenium  and  the  earth  ceria,  and 
isolated  silicon,  thorium,  and  zirconium.  Among  his  students  may  be  men 
tioned  Wohler,  Heinrich  and  Gustav  Rose,  Mosander,  Sefstrom,  and 

Arfwedson. 


"The  chymists  are  a  strange  class  of  mortals  impelled 
by  an  almost  insane  impulse  to  seek  their  pleasure 
among  smoke  and  -vapour,  soot  and  -flame,  poisons 
and  poverty;  yet  among  all  these  evils  I  seem  to  live 
so  sweetly,  that  may  I  die  if  I  would  change  places 
with  the  Persian  King'9  (1 ) 


11 

Tellurium  and  selenium 


It  has  been  shown  in  preceding  chapters  that  a  number  of  ele 
ments  including  zinc,  cobalt,  nickel,  manganese,  hydrogen,  nitro 
gen,  oxygen,  tungsten,  molybdenum,  and  chromium  were  recog 
nized  and  isolated  during  the  eighteenth  century.  The  story  of 
tellurium,  its  discovery  by  Baron  Mutter  von  Reichenstein,  and 
its  confirmation  by  Klaproth  remains  to  be  told.  Although  sele 
nium  properly  belongs  in  the  early  part  of  the  nineteenth  century, 
it  is  so  closely  related  to  tellurium  both  chemically  and  historically 
that  it  seems  best  to  introduce  it  at  this  point.  The  scientific  con 
tributions  and  correspondence  of  Klaproth  and  of  Berzelius  fur 
nish  detailed  information  about  these  two  great  discoveries,  and 
the  "Early  Recollections  of  a  Chemist"  by  Friedrich  Wohler 
present  an  unforgettable  picture  of  the  great  Swedish  master. 


TELLURIUM* 

T 

JL  he  discoverer  of  tellurium,  Franz  Joseph  Miiller,  was  born 
on  July  1,  1740,  in  (Sibiu,  Nagyszeben  or  Hermannstadt)  in  the  Tran- 
sylvanian  Alps  (14).  After  studying  law  and  philosophy  in  Vienna,  he 
attended  the  School  of  Mines  at  Schemnitz  ( Sehneczbanya,  or  Stiavnica 
Banska),  where  he  became  intensely  interested  in  mining,  mineralogy, 
chemistry,  and  mechanics.  At  the  age  of  twenty-eight  years  he  became 
a  surveyor  in  Hungary,  and  two  years  later  he  served  so  efficiently  on  a 
committee  which  managed  the  mines  and  smelters  in  the  Banat  that  he 
was  appointed  surveyor  and  director  of  the  mines.  In  1775  he  went  to 
the  Tyrol  as  mine  captain  and  acting  superintendent,  and  under  Joseph 
II  he  became  chief  inspector  of  all  the  mines,  smelters,  and  saltworks  in 
Transylvania  (2). 

In  1782  Miiller  extracted  from  a  bluish  white  ore  of  gold  (called 
aurum  problematicum,  aurum  paradoxum,  or  aurum  album )  a  metal  which 
A.  von  Rupprecht  thought  to  be  antimony.  Miiller's  paper  announcing 

*  See  also  Chapter  12,  pp.  319ff.  and  ref.  (15),  p.  337. 

303 


304 


DISCOVERY  OF  THE  ELEMENTS 


From  Dr.  Richard  Bright's  "Travels  through 
Lower  Hungary,"  1818 

Schemnitz  ( Selmeczbanya,  or  Stiavnica  Banska).     Franz  Joseph  Muller,  the 
discoverer  of  tellurium,  was  educated  at  the  Schemnitz  School  of  Mines. 


the  discovery  was  entitled,  "An  Experiment  with  the  Regulus  Thought  to~ 
Be  Metallic  Antimony  Occurring  in  the  Mariahilf  Mine  on  Mt  Facebaj 
near  2alatna/'*  Upon  careful  examination  of  the  regulus,  he  decided  in 
1783  that  although  it  bore  some  resemblance  to  antimony,  it  must  be  a 
new  metal,  different  from  all  others.  Seeking  confirmation  of  his  dis 
covery,  he  sent  a  tiny  specimen  to  Torbern  Bergman;  but,  with  such  a 
small  sample,  the  latter  could  do  no  more  than  prove  that  it  was  not 
antimony  (3, 11). 

Miiller's  important  discovery  seems  to  have  been  overlooked  for  fif 
teen  years,  but  on  January  25,  1798,  M.  H.  Klaproth  read  a  paper  on  the 
gold  ores  of  Transylvania  before  the  Academy  of  Sciences  in  Berlin.  He 
reminded  his  hearers  of  the  forgotten  element,  and  suggested  for  it  the 
name  tellurium,  meaning  earth,  by  which  it  has  ever  since  been  known 
(3).  It  is  hard  to  understand  why  so  many  historians  of  science  credit 
him  with  the  discovery  of  tellurium.  Klaproth,  who  was  never  desirous 
of  undeserved  honors,  stated  definitely  that  the  element  had  been  dis 
covered  by  Miiller  von  Reichenstein  in  1782  (11,  14). 

*  "Versuch  mit  dem  in  der  Grube  Mariahilf  in  dem  Gebirge  Facebaf  bei  Zalantna 
vorkommenden  vermeinten  gediegenen  Spiessglaskonig." 


TELLURIUM  AND  SELENIUM  305 

Klaproth  isolated  tellurium  from  the  gold  ore  by  the  following 
method.  After  digesting  the  pulverized  ore  with  aqua  regia,  he  filtered  off 
the  residue  and  diluted  the  filtrate  slightly  with  water.  When  he  made 
the  solution  alkaline  with  caustic  potash,  a  white  precipitate  appeared,  but 
this  dissolved  in  excess  alkali,  leaving  only  a  brown,  flocculent  deposit 
containing  gold  and  hydrous  ferric  oxide.  Klaproth  removed  this  precipi 
tate  by  filtration  and  added  hydrochloric  acid  to  the  filtrate  until  it  was 
exactly  neutral.  A  copious  precipitate  appeared.  After  washing  and 
drying  it  he  stirred  it  up  with  oil  and  introduced  the  oil  paste  into  a 
glass  retort,  which  he  gradually  heated  to  redness,  When  he  cooled  the 
apparatus,  he  found  metallic  globules  of  tellurium  in  the  receiver  and 
retort  (3,11). 

The  discovery  of  tellurium  was  by  no  means  the  only  service  that 
Miiller  von  Reichenstein  performed  for  the  glory  of  his  country.  Kaiser 
Joseph  appointed  him  acting  governor  (Gubernialrath)  and  raised  him 
to  the  hereditary  nobility  with  the  title  of  Freiherr  (Baron)  von  Reichen 
stein.  For  sixteen  years  he  was  a  courtier  in  Vienna,  but  in  1818  he 
asked  permission  to  retire.  Although  he  was  exempted  from  making 
reports,  he  was  still  asked  to  attend  all  the  council  meetings,  in  order  that 
the  state  might  continue  to  receive  his  valued  advice  on  mining  and 
metallurgy.  The  cross  of  the  Order  of  St.  Stephen  was  awarded  to  him 
for  distinguished  services  to  his  country  and  he  was  also  elected  to 
membership  in  the  Mining  Society,  the  Gesellschaft  naturforschender 
Freunde  ( Society  of  Scientific  Friends )  at  Berlin,  and  in  the  Mineralogical 
Society  at  Jena  (2).  After  serving  his  country  for  sixty-two  years  and 
publishing  many  contributions  to  chemistry  and  mineralogy,  Miiller  von 
Reichenstein  died  in  Vienna  at  the  venerable  age  of  eighty-five  years  (4). 

According  to  Paul  Diergart,  Paul  Kitaibel,  professor  of  botany  and 
chemistry  at  the  University  of  Pest,  discovered  tellurium  independently 
in  1789  and  wrote  a  paper  on  it  (5,  14,  15).  This  will  be  discussed  in 
the  next  chapter. 

Natural  Tellurides  in  the  United  States.  F.  A.  Genth  believed  that 
the  name  sylvanite  usually  comprised  two  distinct  minerals,  "graphic 
tellurium/'  for  which  he  retained  the  name  sylvanite,  and  the  "Weisstellur" 
and  "Gelberz,"  which  he  believed  to  be  mechanical  mixtures  of  different 
species  (24).  In  1819  both  tellurium  and  tungsten  were  found  in  some 
of  the  ores  from  Ephraim  Lane's  bismuth  mine  at  Huntington,  Connecti 
cut  (25).  The  first  discovery  of  a  natural  telluride  in  the  United  States 
was  made  in  1848  by  Dr.  C.  T.  Jackson.  His  final  analysis  of  an  ore 
from  the  Whitehall  Mine  in  Spotsylvania  County,  near  Fredericksburg, 
Virginia,  identified  it  as  tetradymite,  bismuth  telluride  (24,  26).  In  1857 
W.  P.  Blake  reported  the  occurrence  of  tellurium  in  an  ore  from  George 
town,  California  (24, 27). 


306  DISCOVERY  OF  THE  ELEMENTS 


From   "Jac.   Berselius,   Selbstbiographische  Aufzeichnungen," 
Kahlbaum  Monographs,  Heft  7 

Yauthtful  Portrait  of  Berzelius?  Left  an  orphan  early  in 
his  life,  he  was  educated  by  his  stepfather.  Berzelius 
studied  at  the  Linkoping  Gymnasium  and  later  at  the 
University  of  Upsala,  where  he  received  the  degree  of 
Doctor  of  Medicine.  He  was  a  student  of  Ekeberg,  the 
discoverer  of  tantalum.  Although  H.  G.  Soderbaum  used 
this  portrait  as  the  frontispiece  to  "Jac.  Berzelius. 
Reseanteckningar"  (Travel  Notes),  Arne  Holmberg 
stated  that  there  is  some  doubt  as  to  its  authenticity. 
See  ref.  (20), 


SELENIUM 

The  discoverer  of  selenium  was  the  illustrious  Swedish  chemist,  Jons 
Jacob  Berzelius,  who  was  born  in  Vaversunda,  a  village  in  Ostergotland, 
on  August  20,  1779.  When  he  was  four  years  old  his  father  died  of 
tuberculosis.  Two  years  later  his  mother  married  Anders  Ekmarck,  pastor 
of  a  German  congregation  at  Norrkoping,  whom  Berzelius  described  long 


TELLURIUM  AND  SELENIUM 


307 


Second-Floor  Plan  of  Ber 
zelius'  Laboratory  and 
Dwelling  House.  I—Kit 
chen-Laboratory.  2— Lab 
oratory.  3— Bedroom.  4— 
Parlor.  5— Not  used  by 
Berzelius. 


after  in  his  autobiography  as  "a  man  of  exemplary  virtue,  of  more  than 
ordinary  learning,  and  gifted  with  a  rare  disposition  for  the  rearing  of 
children.  He  had  been  married  before  and  had  two  sons  and  three 
daughters.  He  was  also  a  good  father  to  his  stepchildren  (Jons  Jacob  and 
his  sister  Floral  Christina)"  (21 ).  When  Ekmarck  was  called  to  be  pastor 
at  Ekeby  and  Rinna  in  the  Linkoping  diocese  and  imparted  the  news  to 
his  wife  as  a  glad  surprise,  the  shock  to  her  nervous  system,  while  she 
was  nursing  their  very  young  child,  was  so  great  that  in  a  few  days  "she 
was  no  longer  among  the  living."  This  tragedy  so  affected  Jons  Jacob, 
who  was  then  about  eight  years  old,  that  throughout  his  entire  life  he 
dreaded  any  sort  of  surprise  (22). 

After  receiving  his  early  education  first  at  the  school  in  Linkoping 
and  then  under  his  stepfather  and  under  tutors,  Berzelius  studied  medi 
cine  at  Upsala,  and  at  the  age  of  twenty-two  years  he  received  his  medical 
degree.  Johan  Afzelius,  a  nephew  of  Torbern  Bergman,  was  then  the 
professor  of  chemistry,  and  A.  G.  Ekeberg,  who  discovered  tantalum  at 
about  the  time  of  Berzelius'  graduation,  was  an  assistant. 

In  the  same  year  Berzelius  was  appointed  adjunct  in  medicine  and 
pharmacy  without  salary  at  the  celebrated  surgical  school  of  Stockholm, 
which  he  served  with  honor  and  distinction  for  the  rest  of  his  life.  During 
part  of  the  time  he  also  lectured  at  the  Military  College  and  at  the  Medico- 
Surgical  Institute  at  Stockholm.  Berzelius,  unlike  other  chemistry  pro 
fessors  of  his  time,  enlivened  his  lectures  with  many  striking  demonstra 
tions.  His  fame  as  a  teacher  soon  spread  throughout  Europe,  with  the 
result  that  brilliant  ambitious  students  of  chemistry  made  Stockholm  their 
Mecca.  Billiard  Mitscherlich,  Friedrich  Wohler,  C.  G.  Gmelin,  C.  G. 
Mosander,  L.  F.  Svanberg,  N.  G.  Sefstrom,  and  the  Rose  brothers,  Heinrich 
and  Gustav,  all  received  their  inspiration  from  the  great  Swedish  master. 
(23)- 


308 


DISCOVERY  OF  THE  ELEMENTS 


Gustav       Magnus,       1802-1870. 

German  chemist  and  physicist. 
One  of  Berzelius'  distinguished 
students.  He  was  one  of  the  first 
chemists  to  investigate  tellurium. 
He  contributed  to  mineralogical 
chemical  analysis,  physiological 
and  agricultural  chemistry,  and 
chemical  technology,  and  devised 
a  simple  process  for  recovering 
selenium  from  the  slime  in  the 
lead  chambers  of  sulfuric  acid 
plants.  He  also  carried  out  im 
portant  researches  in  mechanics, 
hydrodynamics,  heat,  optics,  elec 
tricity,  and  magnetism. 


A  pencil  sketch  by  Magnus's  brother, 
Eduard.  From  Hofmann's  "Zur  Erin- 
nerung  an  vorangegangene  Freunde" 

A  vivid  picture  of  Berzelius  and  an  understanding  of  his  sympathetic 
attitude  toward  his  students  may  be  obtained  by  reading  the  "Early 
Recollections  of  a  Chemist/'  by  Friedrich  Wohler: 

With  a  throbbing  heart  [says  Wohler]  I  stood  before  Berzelius's  door  and 
rang  the  bell.  A  well-dressed,  dignified  gentleman  with  florid  and  healthy 
complexion  let  me  in.  It  was  Berzelius  himself.  He  welcomed  me  very  cor 
dially,  informed  me  that  he  had  been  expecting  me  for  some  time,  and  wished 
me  to  tell  him  of  my  journey— all  this  in  the  German  language,  with  which  he 
was  as  familiar  as  with  French  and  English.  This  first  day  he  took  me  to  the 
Caroline  Institute,  where  he  gave  his  lectures  to  medical  students,  but  which 
were  also  attended  by  officers  of  the  army  and  several  of  his  friends,  and  which 
I  regularly  visited  afterwards  to  accustom  my  ear  to  the  language.  This  af 
forded  me  opportunity  to  admire  his  calm  and  clear  delivery  and  his  skill  in 
performing  experiments.  In  this  institute  was  also  the  laboratory  for  medical 
students,  which  was  presided  over  by  Mosander  (6). 

Berzelius  determined  the  atomic  weights  of  nearly  all  the  elements 
then  known,  and  was  the  first  chemist  to  determine  them  accurately. 
(19).  He  referred  his  atomic  weights  to  oxygen,  which,  however,  he 
allowed  to  equal  100,  instead  of  16  as  in  our  present  system.  In  his  little 
laboratory  that  looked  like  a  kitchen  and  in  which  the  sandbath  on  the 
stove  was  never  allowed  to  cool,  Berzelius  discovered  the  important 
elements:  selenium,  silicon,  thorium,  cerium,  and  zirconium  (18). 

About  a  hundred  miles  northwest  of  Stockholm  there  lies  among 
barren  hills  the  famous  old  mining-town  of  Falun  (or  Fahlun).  The 


TELLURIUM  AND  SELENIUM  309 

average  tourist  might  not  have  been  greatly  interested  in  the  smoky  old 
town  with- its  grimy,  little  wooden  houses,  its  sickly  vegetation,  and  its 
odor  of  sulfuric  acid  fumes,  but  the  chemist  would  recall  its  important 
role  in  the  early  history  of  selenium.  Berzelius  and  Assessor  Gahn  owned 
shares  in  a  sulfuric  acid  plant  at  Gripsholm  that  used  as  raw  material 
pyrite  from  the  mine  at  Falun. 

In  the  summer  of  1817  Berzelius  spent  several  weeks  at  Gripsholm 
with  J.  G.  Gahn  and  Hans  Peter  Eggertz,  working  out  technical  details 
in  the  manufacture  of  sulfuric  and  nitric  acids,  vinegar,  mustard,  soft 
soap,  and  pigments.  On  September  23  he  wrote  to  Trolle-Wachtmeister, 
"We  found  tellurium  at  Gripsholm.  Guess  where?  In  the  sulfuric  acid; 
but  the  quantity  is  very  small"  On  the  same  day  (7)  he  wrote  as  follows 
to  Dr.  Marcet:  "In  a  sulfuric  acid  factory  here,  in  which  Gahn  and  I 
bought  shares,  we  have  recently  found  tellurium  in  the  form  of  sulfur 
mixed  with  sulfuric  acid.  In  plants  of  this  kind,  part  of  the  burning  sulfur 
vaporizes  without  being  oxidized,  and  precipitates  in  the  acid.  It  is  in 
this  deposit  at  the  bottom  of  the  lead  chamber  that  we  have  found  the 
tellurium.  The  sulfur  we  use  is  produced  from  pyrite  from  the  Fahlun 
Mine,  where  tellurium,  however,  has  never  been  found.  In  Fahlun  the 
odor  of  burning  tellurium  blended  with  that  of  sulfur  dioxide  has  some 
times  been  detected,  although  Gahn  never  succeeded  in  pointing  out  any 
trace  of  a  tellurium-bearing  fossil  in  the  Fahlun  Mine'*  (28). 

On  February  6th  of  the  following  year  Berzelius  wrote  again  to  Dr. 
Marcet,  telling  him  that  they  had  been  mistaken  about  the  tellurium  (8) : 

I  have  just  examined  it  more  carefully  here  at  Stockholm  [wrote  Berzelius] 
and  have  found  that  what  Mr.  Gahn  and  I  took  for  tellurium  is  a  new  substance, 
endowed  with  interesting  properties.  This  substance  has  the  properties  of  a 
metal,  combined  with  that  of  sulfur  to  such  a  degree  that  one  would  say  it  is  a 
new  kind  of  sulfur.  Here  are  some  of  its  properties.  ...  If  one  sublimes  it  in  a 
large  vessel,  it  is  deposited  in  the  form  of  flowers  of  a  cinnabar  red,  which  are 
nevertheless  not  oxidized.  During  its  cooling  it  keeps  for  some  time  a  certain 
degree  of  fluidity,  such  that  one  can  shape  it  between  the  fingers  and  draw  it 
into  threads.  .  .  .  When  one  heats  this  new  substance  with  a  flame,  it  burns 
with  an  azure  blue  flame,  and  gives  a  very  strong  odor  of  radishes;  it  was  this 
odor  that  made  us  think  it  was  tellurium. 

The  similarity  to  tellurium  has  given  me  occasion  to  name  the  new  sub 
stance  selenium.  ...  In  the  hope  of  pleasing  you  and  Mr.  Wollaston,  I  am  en 
closing  a  little  thread  of  selenium,  which  will  surely  be  broken  before  arriving, 
but  some  of  it  will  always  remain.  The  paper  in  which  it  is  wrapped  has  been 
colored  by  a  sublimation  of  selenium  which  took  place  when,  in  my  absence, 
the  fire  was  stirred  up  too  much  in  order  to  evaporate  a  solution  of  ammonium 
selenate  (8). 

The  following  long  quotation  from  Berzelius  not  only  gives  the  details 


310 


DISCOVERY  OF  THE  ELEMENTS 


of  this  remarkable  discovery,  but  also  serves  as  a  splendid  example  of  his 
vividly  clear  literary  style: 

They  use  at  Falun  [he  said]  for  the  manufacture  of  sulfur,  pyrites  occurring 
at  various  places  in  the  copper  mine.  The  pyrites  are  often  mixed  with  galena, 
blende,  and  several  foreign  substances.  The  pyrites  are  placed  on  -a  layer  of 
dry  wood,  in  long,  horizontal  furnaces,  the  upper  part  of  which  is  covered  with 
earth  and  decomposed  pyrites;  the  fumes  pass  from  these  furnaces  into  horizon 
tal  tuyeres,  the  fore  part  of  which  is  of  brick  and  the  rest  of  wood.  The  wood  is 
lighted  below,  and  the  heat  causes  the  excess  sulfur  to  distil  from  the  lower  layer 
of  the  pyrite;  the  gaseous  sulfur  is  carried  by  the  current  of  warm  air,  and  is 
finally  deposited  as  flowers  in  the  tuyeres.  .  .  . 

When  this  distilled  sulfur  is  used  for  manuf acturing  sulfuric  acid  by  burning 
it,  a  red,  pulverulent  mass  is  deposited  at  the  bottom  of  the  lead  chamber. 
This  fact  was  observed  long  ago  by  Mr.  Bjuggren,  who  then  owned  a  sulfuric 
acid  plant  at  Gripsholm.  He  found  that  this  does  not  occur  when  another  kind 
of  sulfur  is  used;  and  as  he  had  learned  from  a  chemist  that  the  red  material 
must  contain  arsenic,  he  no  longer  used  sulfur  from  Falun. 

Since  this  plant  has  been  purchased  by  Gahn,  Eggertz  and  myself  [continued 
Berzelius],  the  Falun  sulfur  has  been  burned  there  continually.  The  red  sedi 
ment  which  forms  in  the  acid  liquid  always  remained  at  the  bottom  of  the 
chamber,  and  consequently  increased  in  thickness  to  the  depth  of  a  millimeter. 
The  operation  by  which  the  sulfur  is  acidified  in  this  plant  differs  from  that 
usually  employed  in  that  the  sulfur  is  not  mixed  with  potassium  nitrate.  Flat 


Balances  Used  by  Berzelius 


TELLURIUM  AND  SELENIUM 


311 


From  Guinchard's  "Sweden,"  Vol.  2 

The  Falun  Mine  Is  the  Oldest  Copper  Mine  in  Sweden.  It  was  worked  in 
the  13th  century,  and  has  been  run  almost  continually  ever  since.  Its  present 
output  of  copper  is  small,  but  iron  pyrite  is  still  produced.  The  pyrite  from 
this  mine  was  the  first  source  of  selenium.  Gahn,  the  discoverer  of  man 
ganese,  and  Sefstrom,  the  discoverer  of  vanadium,  lived  in  Falun. 

glass  vessels  containing  nitric  acid  are  placed  on  the  bottom  of  the  tank  and  the 
sulfurous  acid  gas,  in  decomposing  the  nitric  acid,  produces  the  nitrous  gas 
necessary  for  the  complete  acidification  of  the  sulfur.  .  .  . 
Berzelius  then  explained  how  he  and  Assessor  Gahn  had  been  misled 
into  thinking  that  they  had  found  tellurium  in  the  sulfuric  acid: 

In  the  glass  vessels  containing  the  nitric  acid  [said  he]  there  is  found,  after 
the  complete  decomposition  of  the  nitric  acid,  a  concentrated  sulfuric  acid  at 
the  bottom  of  which  is  deposited  a  red,  or  sometimes  brown  powder.  This 
powder  aroused  our  attention  and  led  us  to  make  a  special  examination  of  it. 
The  quantity  resulting  from  the  combustion  of  250  kilos  of  sulfur  did  not  exceed 
3  grams.  The  principal  mass  was  sulfur;  it  could  be  lighted  and  burned 
like  this  substance;  but  it  left  a  copious  ash  which,  when  heated  with  a  blowpipe, 
gave  a  strong  odor  of  decayed  radishes  or  cabbage,  analogous  to  that  which 
Klaproth  says  is  produced  when  one  treats  tellurium  in  the  same  manner.  .  .  . 

The  appearance  of  a  substance  as  rare  as  tellurium  in  the  Falun  sulfur  led  me 
to  try  to  isolate  it,  in  order  to  obtain  more  exact  and  certain  ideas  regarding  it. 
I  therefore  had  the  whole  mass  at  the  bottom  of  the  lead  chamber  removed. 
While  still  wet  it  had  a  reddish  color,  which,  upon  desiccation,  became  almost 
yellow.  It  weighed  about  four  pounds.  It  was  treated  with  aqua  regia  added 
in  sufficient  quantity  to  render  the  mass  pulpy,  and  was  finally  digested  at  a 
moderate  temperature.  It  gradually  changed  color,  the  red  disappeared,  and 


312 


DISCOVERY  OF  THE  ELEMENTS 


Alexandre  Marcet,  1770-1822.  Swiss 
physician  and  chemist.  Lecturer  on 
chemistry  at  Guy's  Hospital,  London. 
Friend  of  Berzelius,  Wollaston,  and  Ten- 
nant.  He  carried  out  a  number  of  re 
searches  in  physiological  chemistry.  In 
collaboration  with  Berzelius  he  studied 
the  properties  of  carbon  disulfide. 


the  mass  became  greenish  yellow.  After  48  hours  of  digestion,  water  and  sul- 
furic  acid  were  added,  and  it  was  filtered.  The  filtrate  had  a  deep  yellow  color. 
The  mass  remaining  on  the  filter  had  not  visibly  diminished  in  volume;  it  con 
sisted  principally  of  sulfur  mixed  with  lead  sulfate  and  other  impurities. 

The  final  steps  in  the  isolation  of  the  new  element  were  described  by 
Berzelius  as  follows: 

A  small  quantity  of  filtrate  [said  he]  was  taken  to  study  the  method  of 
separating  the  substance  supposed  to  be  present;  it  was  precipitated  with  am 
monium  hydroxide.  The  precipitate,  well  washed  and  dried,  mixed  with  potas 
sium  and  heated  at  the  end  of  a  barometer  tube,  decomposed  with  ignition. 
Placed  in  water,  a  part  dissolved,  and  the  liquid  acquired  the  orange  color  of 
strong  beer,  very  different  from  the  red  wine  color  given  by  the  hydrotelluride 
of  potassium.  The  liquid  did  not  cover  the  silvery  pellet  which  always  rises  to 
the  surface  of  the  hydrotelluride  of  potassium;  but  after  a  few  hours,  it  became 
turbid  and  deposited  red  flakes,  the  quantity  of  which  was  increased  by  the 
addition  of  nitric  acid.  The  precipitate  was  preserved,  and  when  a  part  of  the 
filter  on  which  the  red  precipitate  had  been  collected  was  lighted  at  a  candle 
flame,  it  gave  the  edges  of  the  flame  an  azure  blue  color,  meanwhile  exhaling  a 
strong  odor  of  putrid  cabbage.  A  portion  of  very  pure  tellurium,  precipitated 
in  the  same  manner  from  a  solution  of  the  hydrotelluride  of  potassium,  had  a 
gray  color,  gave  a  greenish  color  to  the  edge  of  the  flame,  and  produced  no 
perceptible  radish  odor.  .  .  . 

Berzelius  then  proved  that  the  odor  of  impure  tellurium  is  caused  by 
the  presence  in  it  of  small  amounts  of  the  new  substance; 


TELLURIUM  AND  SELENIUM  313 

Upon  examining  more  carefully  the  purified  tellurium  which  served  for  my 
earlier  experiments  with  the  oxide  of  tellurium  and  hydrogen  telluride  gas 
[said  he]  I  found  that  it  produced  no  odor,  either  when  one  heated  it  with  the 
blowpipe  or  upon  conversion  to  the  oxide,  and  that  the  only  way  to  make  it 
produce  such  an  odor  was  to  heat  it  in  a  glass  tube  closed  with  the  finger,  until 
the  vaporized  metal  escaped  through  a  hole  in  the  softened  glass.  It  then 
burned  in  this  hole  with  a  blue  flame,  giving  an  odor  entirely  analogous  to  that 
of  the  red  substance.  .  .  .  These  experiments  seemed  to  me  to  prove  that  the 
red  substance  could  not  be  tellurium,  but  that  tellurium  itself  contains  varying 
amounts  of  it  according  to  the  care  with  which  it  has  been  purified.  .  .  . 

Berzelius  continued  his  experiments  and  soon  realized  that  he  was 
dealing  with  a  new  element: 

The  brown  material,  insoluble  in  water,  examined  more  carefully  [said  he], 
was  recognized  to  be  the  cause  of  the  peculiar  odor  we  mentioned  above;  and  by 
means  of  some  experiments  which  we  shall  report  soon,  it  was  found  that  it 
was  a  combustible,  elementary  substance  hitherto  unknown,  to  which  I  have 
given  the  name  selenium,  derived  from  Selene  (the  moon),  to  recall  its  analogy 
with  tellurium.  According  to  its  chemical  properties,  this  substance  belongs  be 
tween  sulfur  and  tellurium,  although  it  has  more  properties  in  common  with 
sulfur  than  with  tellurium  (9,  17). 

Since  Klaproth  had  named  tellurium  for  the  earth,  Berzelius  thought 
it  appropriate  to  name  the  sister  element  for  the  earth's  satellite.  The 
results  of  his  investigation  of  selenium  and  its  compounds  were  published 
in  1818  in  the  Annales  de  Chimie  et  de  Physique. 

In  an  attempt  to  trace  selenium  to  its  original  mineralogical  source 
in  nature,  Berzelius  investigated  the  Falun  pyrite,  but  found  that  it  con 
tained  only  0.15  per  cent  of  the  new  element.  He  then  recalled  that  Jan 
(Johan)  Afzelius  had  sent  Assessor  Gahn  a  specimen  of  a  "Swedish 
tellurium  ore,"  which  gave  off  a  radish-like  odor  when  heated  with  the 
blowpipe.  Since  Berzelius  had  never  been  able  to  detect  tellurium  in 
this  ore,  it  now  occurred  to  him  that  it  might  be  a  selenium  mineral. 
Upon  request,  Afzelius  sent  him  a  specimen  of  it.  Berzelius  found  it  to 
be  a  double  selenide  of  silver  and  copper  containing  about  26  per  cent 
of  selenium. 

Although  Afzelius  refused  to  tell  where  he  had  found  the  mineral, 
W.  Hisinger  said  that  it  must  have  come  from  a  deserted  mine  at 
Skrikerum  in  the  North  Kalmar  district.  Berzelius  then  found  specimens 
of  it  from  this  locality  in  the  collections  of  the  Bureau  of  Mines.  Since 
it  had  been  found  at  an  opportune  time,  i.  e.,  in  time  to  be  mentioned  in 
his  original  paper  on  selenium,  he  named  the  mineral  eucairite.  In  the 
same  collection  he  also  found  a  still  richer  selenium  mineral,  a  copper 
selenide  which  is  now  known  as  berzelianite  ( 28 ) . 

In  a  letter  to  Hisinger  on  May  25,  1818,  Berzelius  wrote,  "A  thousand 


314 


DISCOVERY  OF  THE  ELEMENTS 


Reproduced  by  kind  permission  of  the  Edgar  F.  Smith  Memorial  Collection 
in  the  History  of  Chemistry,  University  of  Pennsylvania 

Berzelius  Autograph  Letter.  ( Translation  of  Letter,  Part  of  Which  is  Repro 
duced  Above. )  Letter  of  Introduction  written  by  Berzelius  for  Mr.  Engelke 
to  Herr  E.  L.  Schubarth  Ph.D.,  M.D.,  Professor  Extraordinary  of  Chemistry 
at  the  University  of  Berlin  and  teacher  of  chemistry  at  the  Technical  Institute 

in  Berlin. 

Stockholm,  Apr.  14,  1815. 
Dear  Sir: 

I  herewith  take  the  liberty  to  commend  to  you  heartily  Mr.  Engelke,  the 
bearer  of  this  letter.  Mr.  Engelke  is,  to  be  sure,  really  neither  a  scientist  nor 
a  technologist;  he  is  employed,  however,  in  our  local  Commercial  College, 
where,  because  of  exceptional  general  knowledge  and  great  eagerness  to 
fulfil  his  duties  properly,  he  will  in  time  take  a  higher  place.  The  object  of 
his  present  journey  is  to  study  the  various  industries  in  foreign  countries  from 
the  point  of  view  of  political  economy,  and  indeed  I  could  recommend  him 
to  no  other  than  yourself  with  greater  hope  that  he  would  receive  sound 
guidance  in  these  things.  I  should  therefore  deem  it  a  great  favor  if  you 
would  have  the  kindness  to  receive  my  friend  Engelke  so  that  he  may  have  an 


TELLURIUM  AND  SELENIUM  315 

opportunity  to  see  and  learn  the  things  corresponding  to  the  purpose  of  his 
journey. 

I  beg  you  to  give  my  best  regards  to  [name  illegible]  and,  if  there  is  an 
opportunity,  to  introduce  Mr.  Engelke  to  him. 

With  most  profound  respect,  I  have  the  honor  to  remain,  Sir, 

Your  humble  servant,       JAG.  BERZELIUS 

thanks  for  the  information  about  the  selenium  ore.  I  went  right  up  to 
the  Bureau  of  Mines,  looked  in  their  Skrickerum  (sic)  collection,  and 
found  there  a  good  little  specimen  of  the  fossil  I  called  eucairite  (from 
eukairos,  which  came  in  the  nick  of  time);  there  was  also  a  calcite  pene 
trated  here  and  there  by  a  black  fossil  which  I  found  to  be  a  selenide 
of  copper  with  only  a  trace  of  silver.  .  .  .  Svedenstjerna  also  had  in  his 
collection  some  specimens  from  Skrickerum,  including  the  calcite  pene 
trated  by  copper  selenide"  (29). 

Berzelius's  textbook  of  chemistry  was  translated  into  German  by 
Wohler  and  was  later  translated  into  several  other  languages.  Berzelius 
also  published  each  year,  beginning  in  1821,  a  report  on  progress  in 
physics  and  chemistry  called  the  "Janresbericht  iiber  die  Fortschritte  in 
der  Physik  und  Chemie." 

His  students  and  friends  adored  him.  Although  Friedrich  Wohler 
spent  only  a  few  months  in  Stockholm,  his  contact  with  the  great  master 
influenced  the  whole  course  of  his  life.  Their  frequent  exchange  of 
intimate  letters  lasted  many  years,  to  be  interrupted  at  last  only  by  the 
death  of  Berzelius.  Berzelius'  correspondence  with  Dr.  Alexandre  Marcet, 
Sir  Humphry  Davy,  Dr.  W.  H.  Wollaston,  and  others  was  also  extensive. 

He  did  not  marry  until  late  in  life.  On  January  29,  1836,  he  wrote, 
"Yes,  my  dear  Wohler,  I  have  now  been  a  benedict  for  six  weeks.  I  have 
learned  to  know  a  side  of  life  of  which  I  formerly  had  a  false  conception 
or  none  at  all"  (10).  The  bride  was  more  than  thirty  years  younger  than 
Berzelius,  but  their  married  life  proved  to  be  most  happy.  On  the 
wedding  day  King  Charles  Jean  of  Sweden  honored  him  in  a  gracious  and 
appropriate  manner.  As  Berzelius  entered  his  bride's  home  just  before 
the  ceremony,  his  father-in-law  handed  him  a  letter,  saying  that  the  King 
wished  to  have  it  read  aloud  to  the  guests.  The  letter,  which  was  written 
in  French,  announced  that  Berzelius,  because  of  his  eminent  services  to 
Sweden,  was  to  be  given  the  dignity  and  title  of  Baron  (10,  16). 

Selenium  in  Chile.  In  about  1861  Ignaz  Domeyko,  a  Polish  naturalist 
who  became  professor  of  mineralogy,  geology,  and  physics  at  the  Univer 
sity  of  Santiago,  Chile,  discovered  a  deposit  rich  in  selenides  "in  the 
province  of  Mendoza,  eleven  leagues  southwest  of  the  capital  of  this  name, 
at  the  place  called  Cacheuta,  at  the  lower  part  of  the  Andes."  The 
minerals  included  selenides  of  silver,  copper,  iron,  cobalt,  and  lead,  the 
percentage  of  selenium  varying  between  22.4  and  30.8  per  cent  (30). 


316  DISCOVERY  OF  THE  ELEMENTS 

Crookesite.  In  1866  Baron  Nils  Adolf  Erik  Nordenskiold  found 
among  the  collections  at  the  Royal  Museum  in  Sweden  a  rare  mineral  from 
Skrikerum,  which  C.  G.  Mosander  had  regarded  as  a  copper  selenide. 
When  Baron  Nordenskiold  analyzed  it,  he  found  it  to  be  a  selenide  of 
copper,  silver,  and  thallium.  Because  it  was  the  first  mineral  of  which 
the  recently  discovered  element  thallium  was  shown  to  be  an  essential 
constituent,  he  named  it  crookesite  in  honor  of  Sir  William  Crookes,  the 
discoverer  of  thallium  (31).  Although  crookesite  is  very  rare,  selenium 
and  thallium  are  often  found  associated  in  nature,  and  both  of  these 
elements,  so  different  in  chemical  properties,  were  originally  discovered 
in  the  same  source,  namely  the  slime  in  the  lead  chambers  of  sulfuric  acid 
plants  using  seleniferous  and  thalliferous  pyrite. 

Other  Sources  of  Selenium.  In  1820  Leopold  Gmelin  prepared  pure 
selenium  from  the  fuming  sulfuric  acid  of  Graslitz  [Kretzlitz]  in  Bohemia, 
and  in  the  following  year  Buch  and  Wohler  showed  that  this  selenium 
came  originally  from  the  particles  of  iron  pyrites  dispersed  in  the  alum 
shale  from  which  the  sulfuric  acid  had  been  prepared. 

New  occurrences  of  selenium  were  found  in  rapid  succession.  J.  E. 
F.  Giese  of  Dorpat,  Pleischl  of  Prague,  B.  Scholz  of  Vienna,  W.  Meissner, 
J.  G.  Children,  and  H.  von  Meyer  all  found  it  in  the  deposits  from  various 
kinds  of  sulfuric  acid.  Pleischl  detected  it  in  the  molybdenite  of  Schlag- 
genwald;  F.  Stromeyer,  in  the  volcanic  sal  ammoniac  from  the  Lipari 
Islands;  R.  Brandes,  in  the  volcanic  sal  ammoniac  of  Lanzarote  Island 
(32).  Stromeyer  and  J.  F.  Hausmann,  DuMenil,  J.  B.  Trommsdorff,  J.  K. 
L.  Zincken,  and  Heinrich  Rose  detected  its  presence  in  several  minerals 
(33,34). 

In  1823  Johann  Karl  Ludwig  Zincken  (1790-1862)  detected  selenium 
in  some  ores  from  Zorge  and  Tilkerode  in  the  eastern  part  of  the  Harz, 
and  in  1825  Heinrich  Rose  analyzed  them  quantitatively.  By  heating 
them  in  a  current  of  chlorine  gas,  Rose  converted  all  the  metals  to  chlorides 
and  separated  the  selenium  chloride,  which  was  the  only  volatile  chloride 
present,  from  the  non-volatile  chlorides  of  the  metals  (34).  He  found 
these  minerals  to  be  selenides  of  lead,  copper,  cobalt,  and  mercury. 

On  a  visit  to  the  Harz  in  1830  Berzelius  saw  Zincken's  supply  of 
8x/2  kilograms  of  selenium,  cast  in  ingots,  ready  to  be  sold  at  four 
louis  d'or  per  ounce.  In  hoping  that  perhaps  Zincken  might  like  to 
present  some  selenium  to  him  as  its  discoverer,  Berzelius  was  disappointed. 
Zincken  did  give  him  some  fine  selenium  minerals  however  (35).  Eilhard 
Mitscherlich  also  complained  of  Zincken's  unwillingness  to  share  his 
selenium  with  other  chemists  who  wished  to  investigate  its  properties 
(36). 

In  1828  A.  M.  del  Rio  published  in  the  Philosophical  Magazine  an 
analysis  of  two  new  minerals  containing  zinc,  mercury,  sulfur,  and 


TELLURIUM  AND  SELENIUM  317 

selenium.  These  specimens  had  been  found  by  Jose  Manuel  Herrera  at 
Culebras,  Mexico,  near  the  mining  district  of  El  Doctor  (37).  Del  Rio 
also  mentioned  this  discovery  in  his  "Elements  of  Mineralogy"  (38). 

In  1826  Carl  Kersten  of  Gottingen  detected  selenium  in  the  capillary 
cuprite  or  so-called  copper  bloom  from  Rheinbreitenbach  on  the  Rhine, 
which  Councilor  Hausmann  had  presented  to  him  (39).  He  also  found 
this  element  to  be  present  in  the  earthy  ferruginous  cuprite  (tile  ore)  from 
the  same  locality  (39). 

In  a  postscript  to  Kersten's  article  in  Schweiggers  Journal,  Dr.  Fr. 
W.  Schweigger-Seidel  mentioned  that  "the  efforts  of  mineralogists  and 
chemists  to  locate  selenium  have  nowhere  been  crowned  with  such 
success  as  in  our  Fatherland.  This  is  shown,  among  other  things,  by 
the  circumstance  that  busts  and  pictures  from  Prague  of  the  great 
Swedish  chemist,  cast  in  selenium,  can  be  offered  for  sale  to  his  many 
admirers"  (39).  According  to  Dr.  Arne  Holmberg,  who  has  published 
a  handsome  volume  devoted  to  the  portraits  of  Berzelius,  these  selenium 
medallions  were  made  by  J.  B.  Batka,  a  pharmacist  of  Prague  ( 20 ) . 

Selenium  Poisoning.  Some  soils,  especially  in  the  North  Central 
and  Great  Plains  regions  of  the  United  States,  unfortunately  contain 
selenium.  Many  plants,  when  grown  in  such  soils,  become  toxic  to 
domestic  animals  (40,  41).  In  1917  Th.  Gassmann  showed  that  plants 
can  take  up  selenium  from  the  soil  (42).  According  to  Annie  M.  Kurd- 
Karrer,  "animals  are  far  more  sensitive  to  selenium  than  are  plants. 
Plants  absorb  relatively  large  amounts  without  visible  injury,  and  yet  may 
kill  animals.  The  reverse  is  true  of  boron.  Plants  may  take  up  enough 
of  this  element  to  be  fatally  injured,  yet  they  are  harmless  to  animals" 
(41). 

Henry  G.  Knight,  Chief  of  the  United  States  Bureau  of  Chemistry 
and  Soils,  characterized  selenium  as  "the  first  element  discovered  in  the 
soil  that  seems  to  serve  no  useful  purpose  whatsoever,  even  in  extremely 
small  quantities,  in  the  economy  of  life  except  for  those  plants— "selenium- 
lovers"— which  apparently  grow  and  thrive  only  on  seleniferous  soils. 
To  domestic  plants  and  especially  to  domestic  animals,  it  is  decidedly 
a  health  hazard"  (43).  O.  A.  Beath  observed  in  1932-34  that  the  two- 
grooved  vetch  (Astragalus  bisulcatus)  grown  in  certain  soils  had  an 
offensive  garlic  odor  and  was  more  toxic  and  more  highly  seleniferous 
than  similar  specimens  which  lacked  the  odor.  He  found  that  twenty- 
eight  species  of  Astragalus,  and  certain  other  plants  as  well,  accumulate 
high  concentrations  of  selenium  in  their  tissues  and  thus  serve  as  indica 
tors  for  detecting  seleniferous  soils"  (44). 

Uses  of  Selenium.  Selenium  is  now  used  instead  of  manganese  for 
decolorizing  glass,  and  its  principal  uses  are  in  the  glass  and  ceramics 
industry.  The  metallic  form  of  the  element  is  a  non-conductor  of  elec- 


318  DISCOVERY  OF  THE  ELEMENTS 

tricity  in  the  dark,  but  has  a  conductivity  proportional  to  the  intensity 
of  the  light  falling  on  it.  This  peculiar  behavior  made  possible  the  con 
struction  of  the  very  sensitive  photoelectric  selenium  cell.  The  first 
photophone  using  such  a  cell  for  transmitting  speech  by  means  of  a 
beam  of  light  was  devised  by  Alexander  Graham  Bell  in  1880.  Although 
modern  sound  films  are  made  with  photoelectric  cells  of  the  alkali  metal 
type,  the  early  development  of  talking  pictures,  phototelegraphy,  and 
television  owed  much  to  the  element  that  Berzelius  discovered  in  the 
slime  of  his  sulfuric  acid  plant  (12,  13). 

LITERATURE  CITED 

(1)  BECKER,  J.  J.,  "Acta  Laboratorii  Chymica  Monacensis,  seu  Physica  Subter- 

ranea,"  1669;  H.  E.  HOWE,  "Chemistry  in  Industry/'  3rd  ed.,  Vol.  1,  The 
Chemical  Foundation,  Inc.,  New  York,  1926,  frontispiece. 

(2)  VON  WURZBACH,  C.,  "Biographisches  Lexikon  des  Kaiserthums  Oesterreich," 

60   vols.,    Hof-   und   Staatsdruckerei,    Vienna,    1891.      Article   on    Miiller, 

Freiherr  von  Reichenstein,  Franz  Joseph. 
(5)     JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  Vol.  1,  Baudry  et  Cie.,  Paris,  1891,  pp. 

500-1. 
(4}     POGGENDORFF,   J.    C.,    "Biographisch-Literarisches    Handworterbuch   zur   Ge- 

schichte  der  exakten  Wissenschaften,"  6  vols.,  Verlag  Chemie,  Leipzig  and 

Berlin,  1863-1937.    Article  on  Mtiller  von  Reichenstein,  Franz  Joseph. 

(5)  DIERGART,  P.,  "Tellur  und  Brom  in  der  Zeit  ihrer  Entdeckung,"  Z.   angew. 

Chem.,  33,  299-300   (Nov.,  1920). 

(6)  WOHLER,  F.,  "Early  recollections  of  a  chemist,"  translated  into  English  by 

Laura  R.  Joy.  Am.  Chemist,  6,  131-6  (Oct.,  1875);  "Jugend-Erinnerungen 
eines  Chemikers,"  Ber.,  8,  838-52  (1875). 

(7)  SODERBAUM,  H.  G.,  "Jac.  Berzelius  Bref,"  (Vol.  1,  part  3),  Almqvist  and  Wik- 

sells,  Upsala,  1912-1914,  pp.  157-8. 

(8)  Ibid.,  Vol.  1,  part  3,  p.  161. 

(9)  BERZELIUS,  J,  J.,  "Recherches  sur  un  nouveau  corps  mineral  trouve  dans  le 

soufre  fabrique  a  Fahlun,"  Ann.  chim.  phys.y  9,  160-6  (1818). 

(JO)     WALLACH,  O.,  "Briefwechsel  zwischen  J.  Berzelius  und  F.  Wohler/7  Vol.  1, 
Verlag  von  Wilhelm  Engelmann,  Leipzig,  1901,  pp.  642-3. 

(11)  KLAPROTH,  M.  H.,  "Extrait  d'un  Memoire  de  Klaproth  sur  un  nouveau  metal 

nomine  Tellurium,"  Ann.  chim.  phjs.,  25,  273-81,  327-31  ( 1798 );  ^Abstract 
of  a  memoir  of  Klaproth  on  a  new  metal  denominated  tellurium,"  Nichol 
sons  /.,  2,  372-6  (Nov.,  1798). 

(12)  RANKINE,  "Telephoning  by  light,"  Nature,  104,  604-6  (Feb.  5,  1920). 

(13)  FRIEND,  J.  N-,  "A  Textbook  of  Inorganic  Chemistry,"  Vol.  2,  part  2,  Chas. 

Griffin  and  Co.,  London,  1931,  pp.  297-8  and  301-2. 

(14)  VON  SZATHMARY,  L.,  "Paul  Kitaibel,  the  Hungarian  Chemist,"  Magyar  Gy6gys~ 

ter&sztud.  Tdrsasdg  Ertesitoje,  No.  4, 1-35  ( 1931 ) ;  "Concerning  the  polemics 
which  led  to  the  discovery  of  tellurium,"  ibid.,  No.  1,  1-11  (1932).  In 
Hungarian;  summaries  in  German. 

(15)  WEEKS,  M.  E.,  "The  discovery  of  tellurium,"  /.  Chem.  Educ.,  12,  403-9  (Sept., 

1935). 

(16)  SODERBATTM,  H.  G.,  "Jons  Jacob  Berzelius,  Autobiographical  Notes,"  Williams 

and  Wilkins  Co,,  Baltimore,  1934,  194  pp.  English  translation  by  Olof 
Larsell. 

(17)  BERZELIUS,  J.  J.,  "Undersokning  af  en  ny  mineralkropp  funnen  i  de  orenare 

sorterna  af  det  vid  Fahlun  tillverkade  svaflet,"  Afh.  L  Fysik,  Kemi  och 
Mineralogi,  6,  42-144  (1818). 


TELLURIUM  AND  SELENIUM  319 

(18)  WINDERLICH,  RUDOLF,  "Jons  Jacob  Berzelius,"  /.  Chem.  Educ.,  25,  500-05 

(Sept.,  1948). 

(19)  MACNEVIN,  W.   M.,  "Berzelius.     Pioneer  atomic  weight  chemist,"  /.   Chem. 

Educ.,  30,  207-10  (Apr.,  1954). 

(20)  HOLMBERG,  ARNE,  "Berzelius-portratt,"  Royal  Acad.  of  Sciences  of  Sweden, 

Stockholm,  1939,  pp.  1-2. 

(21)  SODERBAUM,   H.   G.,   "Jac.   Berzelius.      Sjalfbiografiska   anteckningar,"   Royal 

Swedish  Acad.  of  Sciences,  Stockholm,  1901,  246  pp. 

(22)  SODERBAUM,  H.  G.,  "Jac,  Berzelius.    Levnadsteckning/'  Vol.  1,  Royal  Swedish 

Acad.  of  Sciences,  Uppsala,  1929,  p.  18. 

(23)  RHEINBOLDT,  HEINRICH,  "A  vida  e  obra  de  Jons  Jacob   Berzelius/'  Selecta 

Chimica,  9  (1950)  and  10  (1951),  142  pp. 

(24)  GENTH,  F.  A.,  "Contributions  to  mineralogy/'  Am.  J.  Sci.,   (2),  45,  306-20 

(May,  1868). 

(25)  ''Discovery  of  tungsten  and  tellurium/'  ibid.,  (1),  1,  312,  316,  405  (1819). 

(26)  JACKSON,  C.  T.,  "Discovery  of  tellurium  in  Virginia,"  Am.  J.  Sci.,  (2),  6,  188 

(1848);  (2),  10,  78  (1850). 

(27)  BLAKE,  W.  P.,  "Note  on  the  occurrence  of  telluret  of  silver  in  California,"  Am. 

I.  Sci.,  (2),  23,  270-1  (1857). 

(28)  SODERBAUM,  H.  G.?  Ref.  (22),  Vol.  2,  pp.  84-5,  92-7. 

^29)     SODERBAUM,  H.  G.,  Ref.  (7),  Vol.  11,  p.  16;  Vol.  8,  pp.  54-5. 

(SO)     "Enciclopedia  universal  ilustrada  Europeo-americana,"  Vol.  18,  part  2,  Hijos 

de  J.  Espasa,  Barcelona,  no  date  given,  p.  1821.    Biographical  sketch  of  I. 

Domeyko. 

(31)  NORDENSKIOLD,  A.  E.,  "Die  Selenmineralien  von  Skrikerum/*  /.  prakt  Chem., 

102,  456-8  (1867);  Oefvers.  af  Akad.  ForhandL,  1866,  p.  361. 

(32)  VAUQUELIN,  N.-L.,  "Ueber  das  Vorkommen  des  lodins  in  dem  Mineralreiche. 

Nachschrift  des  Dr.  Meissner,"  Schweiggers  /.,  (4),  45,  26-32  (1825). 
Iodine  and  selenium  in  volcanic  sal  ammoniac. 

(33)  STROMEYER,  F.,  "Selenium  in  the  sulphur  of  the  Lipari  Isles/'  Annals  of 

philos.,  n.s.,  10,  233-4  (Sept.,  1825). 

(34)  ROSE,  HEINRICH,  "Analysis  of  the  seleniurets  of  the  Eastern  Harz,"  Annals  of 

philos.,  n.s.,  10,  284-92  (Oct.,  1825). 

(35)  SODERBAUM,  H.  G.,  Ref.  (22),  Vol.  3,  pp.  18-19. 

(36)  SODERBAUM,  H.  G.,  Ref.  (7),  Vol.  13,  p.  195.     Letter  of  E.  Mitscherlich  to 

Berzelius,  Nov.,  1832. 

(37)  DEL  Rio,  A.  M.,  "Analysis  of  two  new  mineral  substances,  consisting  of  bi- 

seleniuret  of  zinc  and  sulphuret  of  mercury,  found  at  Culebras  in  Mexico/ 
PM.  Mag.,  (2),  4,  113-15  (Aug.,  1828). 

(38)  DEL  Rio,  A.  M.,  "Elementos  de  orictognosia,"  2nd  ed.,  John  Hurtel,  Philadel 

phia,  1832,  pp.  484-5. 

(39)  KERSTEN,  CARL,  "Ueber  ein  neues  Vorkommen  des  Selens,"  Schweiggers  /., 

(4),  47,  29^7  (1826);  "Nachschrift  des  Dr.  Fr.  W.  Schweigger-Seidel," 
ibid.,  (4)  47,  297-309  (1826). 

(40)  WOODS,  L.  L.,  "Selenium,  the  new  enigma/'  J.  Chem.  Educ.,  17,  483-4  (Oct., 

1940). 

(41)  HURD-KARRER,  ANNIE  M.,  "Selenium  Absorption  by  Plants,  and  Their  Result 

ing  Toxicity  to  Animals/'  Ann.  Rept.  Smithsonian  Inst.  for  1935,  pp. 
289-302. 

(42)  GASSMANN,  TH.,  "Die  quantitative  Bestimmung  des  Selens  in  Knochen-  und 

Zahngewebe  und  im  Hani/'  Hoppe-Seyler's  Z.  physiol.  Chem.,  98,  182-9 
(1917);  "Zum  Nachweis  des  Selens  in  Menschen-,  Tier-,  und  Pflanzenorgan- 
ismus,"  ibid.,  108,  38-41  (1919). 

(43)  KNIGHT,  H.  G.,  "Selenium  and  its  relation  to  soils,  plants,  animals,  and  public 

health,"  Sigma  Xi  Quarterly,  25,  1-9  (Mar.,  1937). 

(44)  TRELEASE,  S.  F.,  "Bad  earth,"  Sci.  Monthly,  54,  12-28  (Jan.,  1942). 


Courtesy   Dr.    L.    von   Szaihmdry 

Paul  Kitaibel,  1757-1S17.     Hungarian  chemist  and 
botanist  who  anticipated  Klaproth  in  his  researches 
on  tellurium.      The   original  discoverer   o£  this   ele 
ment,  however,  was  Miiller  von  Reichenstein. 


12 

Klaproth-Kitaibel  letters  on  tellurium 


Some  letters  of  Klaproth  and  Kitaibel  which  have  been  carefully 
preserved  in  the  Hungarian  National  Museum  at  Budapest  for 
more  than  a  century  shed  new  light  on  the  early  history  of  the 
element  tellurium  and  reveal  the  characters  of  Baron  Franz  Joseph 
Muller  von  Reichenstein,  who  discovered  it  in  the  gold  ores  of 
Transylvania,  of  Paul  Kitaibel,  who  rediscovered  it,  and  of 
Martin  Heinrich  Klaproth,  who  named  it  and  made  it  known  to 
the  scientific  world.  Since  Professor  Ladislaus  von  Szathmdry's 
excellent  articles  (1)  on  this  subject  are  in  the  Hungarian  language 
and  not  readily  accessible  to  most  chemists,  an  English  translation 
of  the  Klaproth-Kitaibel  correspondence  is  presented  here.  The 
original  letters  of  both  are  in  German. 


he  gold  minues  of  Sacarimb  (Nagyag)  were  discovered  by  aci- 
dent.  A  Roumanian  peasant,  Juon  Armindean,  who  used  to  pasture 
his  pig  in  the  Nagyag  forest,  reported  to  Baron  Ignaz  von  Bom's  father 
that  he  had  seen  flames  breaking  through  a  crevice,  which  had  led  him 
to  believe  that  there  must  be  a  rich  deposit  of  metal  there.  After  years 
of  searching,  Born  found  a  black,  leafy  ore  which  he  at  first  mistook  for 
pyrite  but  which  proved  to  be  rich  in  gold.  He  and  his  partner,  Wild- 
burg,  opened  the  shaft  on  April  8,  1747,  and  named  it  the  "Conception 
of  Maria";  the  Roumanians,  however,  called  it  the  "Gypsy  Shaft,"  for 
a  Gypsy  who  lived  nearby  used  to  repair  the  miners'  tools.  Although 
the  Born  family  had  no  difficulty  in  extracting  the  gold,  they  were  unable 
to  determine  the  composition  of  the  ore,  which,  because  of  its  rarity,  was 
highly  prized  by  collectors.  This  ore  was  found  also  at  Zlatna  and 
Baia  de  Aries,  and  later  in  the  Borzsony  (Metallic)  Mountains  (I). 

Baron  Ignaz  Edler  von  Born  was  born  at  Cluj,  Transylvania,  on 
December  26,  1742,  received  his  elementary  education  at  Hermannstadt 
and  Vienna,  and  was  for  sixteen  months  a  member  of  the  Jesuit  order. 
After  extended  travels  in  several  European  countries,  he  returned  to  his 
mother  country  and  devoted  the  rest  of  his  life  to  natural  science, 

321 


322 


DISCOVERY  OF  THE  ELEMENTS 


From    Szathmdry,    "Magyar    Alkgmistdk" 

Ignaz  Edler  von  Born,  1742-1791.    Distinguished  Transyl- 

vanian   metallurgist,   mineralogist,    and   mining    engineer. 

Kitaibel  found  tellurium  in  a  mineral  which  von  Born  had 

incorrectly  designated  as  argentiferous  molybdenite. 


EXAPROTH-KITAEBEL  LETTERS  ON  TELLURIUM  323 

mineralogy,  and  mining.  On  one  of  his  scientific  trips  through  a  mine, 
he  suffered  an  injury  from  which  he  never  fully  recovered.  Because  of 
his  kind  and  generous  nature  and  his  outstanding  reputation  as  a  scholar, 
Baron  von  Born  had  a  large  circle  of  scientific  disciples.  He  was  an 
active  member  of  the  Masonic  Order,  and  founder  of  its  important  but 
short-lived  periodical  Physikalische  Arbeiten  der  eintrdchtigen  Freunde 
in  Wien  ( Physical  Researches  of  the  Harmonious  Friends  in  Vienna ) ,  of 
which  only  two  volumes  were  ever  published.  Baron  F.  J.  Mizller  von 
Reichenstein's  first  papers  on  tellurium  were  published  in  this  rare 
periodical  (13).  Baron  von  Bom's  greatest  contribution  to  mining  was 


Professor   Ladislaus    von    Szathmary. 

Hungarian  historian  of  chemistry  and 
editor.  Author  of  many  articles  and 
books  on  the  history  of  alchemy,  iatro- 
chemistry,  pure  and  applied  chemis 
try,  and  pharmacy.  In  Hungarian  his 
name  is  written:  Szathmary  Laszlo. 


his  improved  hot  amalgamation  process  of  extracting  precious  metals 
from  ores. 

One  of  Baron  von  Bern's  intimate  friends  was  the  famous  world 
traveler  Georg  Forster.  An  entry  in  Forster's  diary  for  July  31,  1784, 
depicts  Bora's  social  circle  as  "a  society  of  seventeen  lively,  vivacious, 
friendly  people  bound  together  by  love  and  friendship,  whose  custom 
it  is  to  scatter  the  seeds  of  enlightenment,  to  resist  prejudices,  and, 
above  all,  to  speak  and  think  candidly.  Since  it  was  Ignatius  Day,  the 
name  day  of  our  dear  Born  was  being  celebrated.  .  .  .  The  love  which 
everyone  here  has  for  him  is  indescribable.  He  is  a  father  among  truly 
loving  and  beloved  children"  (14). 


324 


DISCOVERY  OF  THE  ELEMENTS 


In  the  latter  part  of  the  eighteenth  century,  a  skillful  Hungarian 
chemist,  Colonel  Joseph  Ramacsahazy,  examined  the  gold  ores  of  the 
Borzsony  Mountains  and  was  hampered  in  his  analyses  by  the  presence 
of  a  troublesome  unknown  substance.  In  describing  this  ore  he  used  the 
alchemistic  term  "unripe  gold,"  and  on  January  30,  1781,  he  made  a 
contract  with  another  chemist,  Matthew  Bohm,  to  "ripen"  it.  Bohm  de 
ceived  him,  however,  and  was  deported  from  Hungary.  (This  informa 
tion  was  generously  contributed  by  Professor  von  Szathmary,  who  ob 
tained  it  from  the  Record  Office  in  Budapest. ) 


Courtesy  Prof.  L.  von  Szathmary 

Tellurium  Medallion.  A  very  rare  tellurium  medallion 
bearing  on  one  side  the  inscription  "Tellurium  from  Nagyag, 
1896"  and  on  the  other  the  words  "Royal  Hungarian  Smelter 
at  Selmeczbanya  [Schemnitz]/*  The  diameter  is  43  mm., 
the  thickness  5.5  mm.  One  of  these  medallions  is  owned  by 
the  Hungarian  National  Museum,  another  by  the  University 
of  Sopron  [Odenburg]. 


At  the  Maria  Loretto  shaft  near  Zalatna  in  the  Facebaj  Mountains 
(lower  Fejer  County),  another  white,  leafy  gold  ore  known  as  Spiessglas- 
konig  or  argent  molybdique  presented  similar  difficulties.  When  Pro 
fessor  Anton  von  Rupprecht  of  Selmeczbanya  (Schemnitz)  roasted  the 
mineral  gently  on  charcoal,  he  found  that  the  metallic  residue,  when 
treated  with  mercury,  gave  no  trace  of  vermilion  (red  mercuric  sulfide). 
Since  the  mineral  had  a  metallic  luster,  gave  no  test  for  sulfur,  and  be 
haved  in  many  respects  like  antimony,  von  Rupprecht  concluded  that 
it  must  be  native  antimony. 


KLAPROTH-KITAIBEL  LETTERS  ON  TELLURIUM 


325 


This  view,  however,  was  opposed  by  a  distinguished  contemporary. 
Baron  Franz  Joseph  Miiller  von  Reichenstein  was  born  at  Sibiu,  ( Nagy- 
szeben  or  Hermannstadt )  in  the  Transylvanian  Alps  on  July  1,  1740.* 
After  receiving  his  elementary  education  in  his  native  city,  he  went  to 
Vienna  to  study  philosophy  and  law.  Later  he  became  so  deeply  inter 
ested  in  mining,  metallurgy,  and  chemistry  that  in  1763  he  entered  the 
famous  School  of  Mines  of  Selmeczbanya,  or  Schemnitz  (which  is  now 
known  as  Stiavnica  Banska,  Czechoslovakia).  Here  he  studied  under 
the  capable  leadership  of  N.  J.  Jacquin  (1). 

Upon  returning  to  Transylvania,  he  served  on  a  mining  commission 
to  reorganize  the  neglected  mines  of  his  native  country,  and  later  be 
came  director  of  mines  in  the  Banat.  When  he  succeeded  in  putting  the 
mines  on  a  paying  basis,  Maria  Theresia  entrusted  him  with  similar 


Selenium  Medallion.  A  selenium  medallion 
bearing  a  portrait  o£  Berzelius.  The  diameter  is 
about  45  mm.  This  medallion  was  cast  at  the 
Selmeczbanya  smelter  and  is  now  in  possession 
of  the  University  of  Sopron.  It  is  extremely  rare 
and  has  unfortunately  been  broken. 


Courtesy  Prof.  L.  von  Szaihmary 


responsibilities  in  the  Tyrol.  In  1775,  although  successfully  established 
as  a  mining  official  in  the  little  Tyrolian  town  of  Schwatz,  he  preferred 
to  return  to  his  own  country.  King  Joseph  II  gratified  this  desire  by 
sending  him  to  Transylvania  on  special  commissions,  and  in  1778  ap 
pointed  him  as  provincial  commissioner. 

During  his  travels  Miiller  amassed  a  splendid  mineral  collection, 
which  he  arranged  according  to  Born's  system.  When  he  set  to  work  in 
his  poorly  equipped  laboratory  at  Sibiu  to  examine  the  ore  which 
von  Rupprecht  believed  to  be  native  antimony,  he  made  slow  progress. 
On  September  21,  1782,  however,  he  published  a  statement  (2)  to  the 
effect  that  the  mineral  in  question  was  not  native  antimony,  but  bismuth 

*  This  statement  may  serve  as  a  correction  to  page  65  of  the  first  and  second  editions  of 
"The  Discovery  of  the  Elements."  Dr.  Speter  and  Professor  von  Szathmary  kindly 
informed  me  that  Baron  von  Reichenstein  was  born  in  Nagyszeben  (Sibiu),  not  in 
Vienna,  and  that  he  at  first  mistook  the  tellurium  not  for  antimony  but  for  bismuth. 


326  DISCOVERY  OF  THE  ELEMENTS 

suffide  When  the  ore  was  melted  with  niter  and  tartaric  acid,  it  did 
not  yield  antimony.  It  colored  the  flame  blue  and  formed  an  amalgam 
with  mercury,  whereas  antimony  would  have  failed  to  give  these 

reactions.  . 

In  the  following  year,  however,  he  concluded  that  the  mineral  con 
tained  neither  bismuth  sulfide  nor  antimony,  that  the  gold  was  an  essen 
tial  constituent  of  it,  and  that  it  contained  an  unknown  metal.  In  an 
investigation  lasting  three  years  and  consisting  of  more  than  fifty 
tests  he  determined  the  specific  gravity  of  the  mineral  and  noted  the 
radish  odor  of  the  white  smoke  which  passed  off  when  the  new  metal 
was  heated,  the  red  color  which  the  metal  imparts  to  sulfuric  acid,  and 
the  black  precipitate  which  this  solution  gives  when  diluted  with 

water  (3). 

Miiller  also  sent  a  very  small  specimen  of  the  new  substance  to  lor- 
bern  Bergman,  who  regularly  corresponded  with  him  and  whom  he  con 
sidered  to  be  "the  greatest  chemist  of  the  present  century."  In  the  reply 
dated  April  13,  1784,  Bergman  confirmed  Miiller  s  results,  mentioned 
Elhuyar  s  recent  discovery  of  tungsten,  commented  on  the  surprising 
increase  in  the  number  of  known  metals,  and  added,  "I  am  waiting  im 
patiently  for  your  parcel  so  that  I  may  work  with  larger  amounts. 
Unfortunately,  Bergman  was  never  able  to  work  with  this  larger  speci 
men,  for  he  died  in  July  of  the  same  year.  Twelve  years  later,  Miiller, 
desirous  of  still  further  verification,  sent  a  specimen  to  Martin  Heinrich 
Klaproth,  the  leading  analytical  chemist  of  Germany,  who  analyzed  it  and 
completely  confirmed  the  discovery  of  the  new  metal  (4}.  In  his  report 
before  the  Academy  of  Sciences  in  Berlin  on  January  25,  1798,  Klaproth 
named  the  metal  tellurium  and  mentioned  that  the  original  discoverer  of 
it  was  Miiller  von  Reichenstein. 

When  Miiller  was  promoted  to  the  office  of  aulic  councilor  he  re 
gretfully  left  Transylvania  for  Vienna.  He  was  later  pensioned  with 
the  order  of  St.  Stephen.  He  died  in  Vienna  on  October  12,  1825  (or 
1826?).  Although  Baron  von  Reichensten's  wife,  Margaretha  von  Hoch- 
engarten,  was  German,  and  although  he  spent  much  of  his  life  among 
German  people  and  received  many  honors  from  the  Austrians,  his 
descendants  still  live  in  his  native  land  of  Transylvania. 

In  1789  the  famous  Hungarian  scientist  Paul  Kitaibel  discovered 
tellurium  independently.  He  was  born  on  February  3,  1757,  at  Nagy- 
Marton  ( Matter  sdorf),  and  attended  the  academy  at  Raab  in  order  to 
prepare  himself  for  the  University  of  Buda.  After  serving  under  Profes 
sor  J.  Winterl  as  adjunct  in  chemistry  and  botany  (5,  6),  he  received  his 
medical  degree  in  1785. 

Four  years  later  young  Dr.  Kitaibel  found  a  new  element  in  an  ore 
from  Deutsch-Pilsen  which  Baron  von  Born  had  regarded  as  argentiferous 


KLAPROTH-KITADBEL  LETTERS  ON  TELLURIUM 


327 


molybdenite.  At  the  suggestion  of  Abbe  Estner*  and  Mine  Captain 
Haidinger,1"  he  also  investigated  the  aurum  problematicum  and  found 
that  it  contained  the  same  new  element  as  that  in  the  molybdic  silver. 
When  he  sent  an  account  of  his  researches  to  Klaproth  for  criticism,  the 
latter  gave  a  most  favorable  written  report,  but  evidently  gave  no  further 
thought  to  the  matter.  Mtiller  von  Reichenstein  later  presented  Klaproth 
with  his  supply  of  aurum  problematicum,  and  Klaproth  reported  the  ex- 


)k^«     -^jljjjIjA  s?i|il§i!i|S|SSiSlig$iiiis?S;lis!,   i;jli||;3|/ipS|;SS|l|||, 


Courtesy  Dr.  F.  Fiala 

The  Former  School  of  Mining  and  Forestry  at  Schemnitz, 
or  Selmeczbanya.  Schemnitz,  or  Stiavnica  Banska,  Czecho 
slovakia,  where  Miiller  von  Reichenstein,  the  discoverer  of 
tellurium,  was  educated.  When  Austria-Hungary  was  di 
vided  in  1918,  the  collections,  the  library,  the  archives,  and 
most  of  the  portable  equipment  at  the  former  Schemnitz 
School  of  Mines  were  taken  to  the  University  of  Sopron  in 
Hungary.  Transylvania,  with  its  historic  mines  of  gold  and 
tellurium,  became  part  of  Roumania. 


istence  of  the  new  metal,  tellurium,  giving  full  credit  to  the  original  dis 
coverer.,  Miiller  von  Reichenstein,  but  failed  to  mention  Kitaibel's  work 
on  the  "molybdic  silver."  Since  Kitaibel  was  unaware  of  the  researches 
of  Miiller  von  Reichenstein  and  had  been  led  to  the  erroneous  conclusion 
that  Klaproth  had  claimed  the  discovery,  he  defended  his  priority  over 
the  latter  in  the  following  letter  to  Johann  Georg  Lenz,  professor  of 
mineralogy  at  Jena  (7): 

*  Abbe  Franz  Joseph  Anton  Estner  (1739-1803).     Mineralogist  at  Vienna. 

t  Karl  Haidinger  ( 1756-1797 ) .     Austrian  mineralogist  and  mining  engineer.     Father 

of  the  famous  mineralogist,  Wilhelm  Karl  von  Haidinger. 


328 


DISCOVERY  OF  THE  ELEMENTS 


March,  1800. 

I  received  yesterday  the  diploma  which  the  Mineralogical  Society  at  Jena 
intended  for  me  and  which  you  were  so  kind  as  to  send  me.  I  hasten  to  give 
you  my  heartiest  thanks  and  to  ask  you  to  express  my  gratitude  to  the  famous 
Society  for  this  honor  and  to  assure  it  that  I  shall  strive  to  the  best  of  my  ability 
to  live  up  to  your  mutual  aims.  At  present,  to  be  sure,  I  am  so  occupied  with 
the  duties  of  my  office,  traveling,  and  botanical  work  that  I  scarcely  have  time 
to  think  of  other  activities,  and  my  field  is  not  so  much  mineralogy  as  botany 
and  chemistry;  however,  since  I  hope  to  find  much  worthy  of  notice  on  my  trips 


Courtesy  Dr.  F.  Fiala 


"Belhazy."  The  building  at  Stiavnica  Banska,  Czechoslo 
vakia,  which  in  the  eighteenth  century  housed  the  chemical 
and  mineralogical  laboratories  of  the  former  Schemnitz 
School  of  Mines.  Miiller  von  Reichenstein,  the  discoverer  of 
tellurium,  and  A.  M.  del  Rio,  the  discoverer  of  vanadium, 
both  attended  this  school 


now  about  to  be  taken  at  public  expense,  and  since  the  chemical  analysis  of 
mineral  products  not  yet  sufficiently  well  known  will  be  no  less  welcome  to  the 
Society  than  the  external  characteristics  of  the  same,  I  yet  hope,  when  time  per 
mits,  to  accomplish  some  things  suited  to  your  aims. 

On  this  occasion  I  learned  that  the  news  has  been  brought  to  Jena  that  I 
had  discovered  tellurium  before  Klaproth  and  that  this  famous  chemist  had 
appropriated  my  discoveiy  to  himself.  The  whole  matter  stands  as  follows: 

About  twelve  years  ago,  the  professor  of  natural  history,  Filler,*  who  died 
here,  gave  me  a  little  piece  of  ore  from  Deutsch-Pilsen  in  the  Hont  region,  say 
ing  that  it  was  argentiferous  molybdenite  and  that  I  might  determine  the  silver 
content.  In  some  experiments  that  I  made  with  i,  I  found,  to  be  sure,  that  it 

*  Mathias  Filler  ( 1733-1788),  professor  of  natural  history  at  Buda. 


KLAPROTH-KITAIBEL  LETTERS  ON  TELLURIUM:  329 

did  contain  silver  (8),  but  it  was  evident  also  that  the  remainder  was  certainly 
not  molybdenite,  but  a  new  metal.  After  some  time,  I  found  the  same  mineral 
listed  in  Bern's  Catalogue  as  molybdic  silver. 

When  Abbe  Estner  came  here  to  appraise  the  collection  of  natural  history 
specimens  left  by  Filler,  and  I  learned  that  this  very  expert  mineralogist  was 
working  on  a  Mineralogy,  I  told  him  what  I  had  found  out  experimentally  about 
the  so-called  molybdic  silver  and  what  I  believe  it  to  be.  At  his  request,  I 
repeated  my  previous  experiments  with  the  few  fragments  of  this  mineral  which 
I  still  had,  compiled  [the  results],  and  sent  them  to  him  in  Vienna.  The 
sagacious  mineralogist  and  Mine  Captain  Haidinger,  who  had  an  opportunity 
to  read  my  article,  wrote  me  after  a  time  that  they  believed  that  the  Transylva- 
nian  gold  ores  (aurum  graphicum,  aunnn  problematicum]  contain  the  same 
metal  which  I  had  found  in  Bern's  molybdic  silver;  I  wished  to  investigate  the 
matter  more  thoroughly  and  found  indeed  that  the  metal  which  was  combined 
with  the  gold  in  the  ore  possessed  all  the  properties  found  for  that  in  the  ore 
from  Pilsen,  which  I  immediately  reported  to  Abbe  Estner. 

Some  time  after  this,  Klaproth's  analysis  of  the  molybdic  silver  appeared. 
To  my  no  slight  surprise,  I  found  there  the  statement  that  this  contains  bismuth. 
Mr.  Klaproth  then  came  to  Vienna,  and  Abbe  Estner  gave  him  my  paper  to  read, 
which  was  returned  to  me  with  a  very  favorable  utterance  regarding  my  chemi 
cal  work.  After  this,  Mr.  Klaproth  announced  his  discovery  of  tellurium.  From 
this  it  can  certainly  be  surmised  with  some  foundation  that  this  famous  chemist 
was  led  to  this  discovery  through  my  work,  yet  it  cannot  be  proved;  and  even  if 
the  documents  which  I  possess  were  sufficient  for  this,  yet  I  would  not  do  it. 
Mr.  Klaproth,  with  whom  I  had  the  honor  to  become  personally  acquainted  in 
Berlin  a  year  and  a  half  ago,  is  my  friend,  who,  it  is  to  be  hoped,  will  himself, 
when  he  announces  his  corrected  analysis  of  the  molybdic  silver,  state  to  the 
public  that  I  discovered  the  aforementioned  new  metal  in  this  mineral  before 
he  did.  If  he  does  not  do  this,  Abbe  Estner  will  do  it  when  he  comes  to  this 
subject  in  the  edition  of  his  Mineralogy.  Then  one  may  judge  from  Klaproth's 
behavior  as  one  will;  as  long  as  I  shall  not  have  been  the  cause  of  it,  it  will  not 
trouble  me.  But  until  then  I  must  ask  that  no  public  use  of  information  on  this 
matter,  either  from  my  family  or  from  friends,  shall  be  made;  the  circumstances 
of  my  office  demand  this. 

I  cherish  the  hope  that  some  time  I  may  merit  your  highly  desired  friend 
ship,  and  remain,  Sir,  your  most  respectful  and  obedient  servant, 

K[itaibel]. 

The  following  is  a  translation  of  the  "very  favorable  utterance"  of 
Klaproth  to  which  Kitaibel  referred  in  the  preceding  letter: 

Vienna,  Aug.  1,  1796. 

I  have  read  both  of  the  present  chemical  articles  which  Abbe  Estner  kindly 
communicated  to  me  with  so  much  the  greater  pleasure  because  these  give 


330  DISCOVERY  OF  THE  ELEMENTS 

praiseworthy  evidence  that  the  author  of  them  is  a  thoroughly  practical  chemist. 
The  first  of  these,  concerning  molybdic  silver,  is  not,  to  be  sure,  in  entire  agree 
ment  with  my  results;  but  this  is  easily  explained,  for  my  results  for  these  con 
stituents  refer  only  to  the  individual  specimen  which  I  analyzed.  .  .  . 

Klaproth. 

[The  portion  of  the  report  here  omitted  refers  to  Kitaibel's  paper  on 
hydroferrocyanic  acid  and  Prussian  blue.] 

One  day  as  Klaproth  was  reading  C.  M.  Wieland's  New  German  Mer 
cury,  he  ran  across  the  following  disconcerting  statement  ( 9 ) : 

The  discovery  of  the  new  metal  tellurium,  which  has  already,  in  the  first 
volume  of  the  Zeitschrift  filr  Ungarn,  been  claimed  by  Professor  von  Schedius* 
for  our  energetic  fellow-countryman  Kitaibel  (adjunct  at  the  Hungarian  Uni 
versity  at  Pest)  will  also  soon  be  claimed  for  Mr.  Kitaibel  in  the  second  volume 
of  the  Annalen  der  Jenaischen  Gesellschaft  fur  die  gesammte  Miner alogie. 
Mr.  Klaproth  in  Berlin,  who  has  hitherto  been  regarded  in  Germany  as  the  dis 
coverer,  was  merely  led  by  some  of  Kitaibel's  articles  which  he  read  on  a  visit  to 
Vienna  to  the  further  investigation  of  the  new  metal,  which  he  named  tellurium. 
Suum  cuique! 

As  a  result  of  this  unjust  accusation  Klaproth  wrote  to  Kitaibel  as 
follows: 

Berlin  Sept.  2,  1803. 

Highly  esteemed  Colleague:  It  gives  me  special  pleasure  to  address  you 
by  this  title,  for  on  February  22nd  of  this  year  the  Society  of  Scientific  Friends 
of  this  place  elected  you  as  a  foreign  member.  The  sending  of  the  diploma  has 
up  to  the  present  been  delayed  merely  because  Professor  Willdenow,t  who  is 
taking  charge  of  it,  wishes  to  include  a  few  books  at  the  same  time.  In  the 
meantime,  they  are  ready,  as  Count  von  Waldstein*  has  noted  in  the  preface  to 
Volume  4B  of  our  New  Publications. 

In  proportion  as  this  occasion,  like  all  other  opportunities  for  friendly  cor 
respondence  with  foreign  friends  and  members  of  our  Society,  has  been  pleasant 
and  welcome  to  me,  just  so  deeply  do  I  regret  that  this  my  first  letter  to  you 
also  concerns  at  the  same  time  an  unpleasant  matter.  Only  within  the  last  few 
days  have  I  seen  the  fourth  issue  for  1803  of  Wieland's  New  German  Mercury, 
in  which,  to  my  greatest  astonishment,  I  find  myself  accused,  under  the  heading: 

*  Ludwig  von  Schedius  (1768-1847).     Hungarian  writer,  editor,  cartographer,  and 

humanitarian. 

f  Karl  Ludwig  Willdenow   (1765-1812).     German  botanist  who  studied  chemistry 

under  Klaproth. 

t  Franz  de  Paula  Adam  Graf  von  Waldstein  (1759-1823).     Austrian  botanist  and 

philanthropist. 


KLAPROTH-KITAIBEL  LETTERS  ON  TELLURIUM  331 

"Further  News  of  Hungary's  Most  Recent  Literature  and  Culture,"  of  down 
right  theft;  in  other  words,  of  having  robbed  you  of  the  discovery  of  tellurium!! 
You,  my  dear  colleague,  will  understand  that  I  can  by  no  means  allow  this  insult 
to  my  honor  and  staining  of  my  reputation  to  pass  unnoticed. 

To  be  sure,  I  do  remember  that  a  chemical  paper  was  handed  to  me  in 
Vienna  with  the  request  for  my  opinion  of  it,  which  resulted  favorably.  How 
ever,  as  far  as  the  subject  matter  of  it  is  concerned,  this  I  have  completely  for 
gotten,  and  the  person  who  could  inform  me  is  Estner,  who  is  now  dead.  But, 
on  my  honor,  and  by  all  that  an  honest  man  holds  sacred,  I  assure  you  that  that 
paper  did  not  have  the  slightest  influence  on  my  chemical  experiment  with 
tellurium. 

Long  before  my  trip  to  Vienna,  I  had  worked  on  this  investigation,  using  a 
specimen  which  had  been  sent  here  by  the  late  Mr.  von  Fichtel*  to  Mr.  Sieg- 
friedt;  I  am  also  indebted  to  Mr.  Muller  von  Reichenstein,  who  was  then  in 
Zalathna,  for  voluntarily  sending  me  his  supply  of  tellurium  ores,  which  enabled 
me  to  carry  my  earlier  investigations  farther. 

I  urgently  request  and  expect  a  prompt  and  obliging  reply  in  order  to 
learn  whether  you  yourself  will  be  so  good  as  to  arrange  that  a  public  denial 
of  this  accusation  of  plagiarism  made  against  me  may  be  made  as  soon  as 
possible;  which  I  shall  regard  as  valuable  evidence,  not  so  much  of  your  own 
love  of  truth,  which  I  by  no  means  question,  as  of  your  friendly  and  fraternal 
attitude  toward  me. 

With  the  best  regards  of  all  the  regular  members  of  our  Society,  I  have  the 
honor  to  be,  Sir, 

Your  obedient  friend  and  colleague, 

(Signed)  Klaproth. 
Royal  Chief  Counselor  of  Medicine  and  Sanitation 

Kitaibel  replied  as  follows: 

Sept.  19,  1803. 

Highly  Esteemed  Colleague: 

I  received  your  letter  [of  September  2nd,  1803]  only  day  before  yesterday. 
Pleased  though  I  was  at  first  to  see  your  esteemed  name  signed  to  it,  yet  all  the 
more  deeply  was  I  disconcerted  over  the  real  occasion  for  it:  partly  because  I 
now  truly  believe  that  you  have  been  unjustly  insulted;  partly  because  your  de 
mand  places  me  in  an  embarrassing  situation  from  which  I  do  not  know  how  to 
extricate  myself.  In  order  to  enable  you  yourself  to  judge  of  this  matter  and  of 
what  can  be  done  to  ease  your  mind,  I  must  make  you  better  acquainted  with 
all  the  details,  which  perhaps  you  do  not  yet  correctly  know. 

I  discovered  tellurium  in  1789  in  Bern's  so-called  molybdic  silver.  The 
following  year  I  mentioned  it  verbally  to  Mr.  Estner  and  after  some  time  sent 

*  Johann  Ehrenreich  von  Fichtel  ( 1732—1795 ) .     Hungarian  mineralogist, 
t  Friedrich  Wilhelm  Siegfried  (1734-1809).    German  mineralogist. 


332  DISCOVERY  OF  THE  ELEMENTS 

him  at  his  request  a  written  article  on  the  experiments  I  had  made  with  this 
metal.  He  and  Mine  Captain  Haidinger  expressed  to  me  the  opinion^ that  the 
metal  I  had  discovered  probably  lay  hidden  also  in  the  [nagyagite]  Transyl 
vanian  gray  gold"  (as  Born  called  the  ores  containing  this  tellurium),  whereby 
I  was  led  to  find  this  metal  also  in  the  aforementioned  ores,  of  which  Estner  and 
Haidinger  immediately  received  notice.  The  announcement  of  this  discovery 
was  delayed  by  circumstances  which  need  not  be  mentioned  here. 

Then  you  came  to  Vienna,  obtained  from  Estner  my  article  on  the  investi 
gation  of  the  so-called  silver  molybdenite  and  another  one  on  hydroferrocyamc 
acid  prepared  in  the  free  state,  for  your  opinion,  and  Estner  sent  me  your  written 
verdict  with  the  information  that  he  had  also  communicated  to  you  my  report  on 
the  metal  which  lay  hidden  in  Transylvanian  gold  ores  and  had  requested  you 
to  investigate  the  matter  further.  I  rejoiced  over  this  all  the  more  because  I 
had  good  reason  to  hope  that,  when  you  announced  your  investigation,  you 
would  mention  my  work.  .  . 

When  I  came  to  Vienna  in  the  following  year,  your  discovery  of  tellurium 
was  just  being  read,  and  Estner  said  that  he  was  greatly  surprised  that  you  had 
made  absolutely  no  mention  of  my  report  which  had  been  communicated  to  you. 
"it  was  also  mentioned  in  presence  of  others,  wherefrom  I  suspected  no  conse 
quences  whatever.  After  a  long  time  I  was  also  questioned  verbally  about  the 
details  of  the  affair,  and  a  foreigner  also  sent  me  a  written  inquiry.  Without 
knowing  how  they  had  learned  of  the  matter,  I  answered  according  to  my  knowl 
edge  and  belief.  I  now  see,  to  be  sure,  that  it  would  have  been  better  if  I  had 
suppressed  what  I  knew;  but  you  see,  too,  that  we  were  both  wrong,  you  in 
that  you  did  not  mention  what  you  had  learned  of  my  discoveries  through  Mr. 
Estner-  and  I,  in  that  I  mentioned  what  I  knew. 

You  will  understand  that  it  is  now  difficult  to  set  matters  right.  I  cannot 
say  that  you  knew  nothing  of  my  experiments;  my  article  dated  by  Estner,  your 
written  statement,  and  Estner's  letter  prove  the  contrary  H  you  were  to  say 
that  you  had  forgotten  about  it  and  had  already  made  the  discovery  earlier  I 
and  many  others'would  not  doubt  it,  ^^..^J5.»f^rj± 


an    many  , 

you  before  all  men;  although  no  one  would  have  doubted 

had  previously  said  that  you  had  made  it  before  your  trip  to  Vienna.    If  I  were 

to  say  that  the  details  of  the  matter  were  other  than  what  I  have  just  written 

and  which  are  already  known,  I  would  be  contradicting  myself  and  speaking 


Under  such  circumstances  I  do  not  know  what  you  mean  by  a  public  denial 
which  you  demand  of  me.  I  can  give  you  a  statement  that  my  two  papers 
which  Ibbe  Estner  gave  you  in  Vienna  for  your  verdict  were  not  concerned  wrth 
the  tellurium  of  the  Transylvanian  gold  ore  but  with  Boms  molybdic  silver 
and  free  hydroferrocyanic  acid;  I  can  add  that  I  believe  that  you  ^covered 
tellurium  without  knowing  anything  about  my  researches,  if  that  wiU  satisfy 
you  If  you  can  with  justice  demand  more,  I  ask  you  to  mention  it  and  you 
wm  always  find  ...  me  ready  to  do  everything  which  your  honor  demands 
IS  mm^ermits,  for  I  willingly  believe  you  That  you  forgot  th,  ;  co«  of 
my  paper,  that  you  discovered  tellurium  without  knowing  anything  about  this, 


KLAPROTH-KITATBEL  LETTERS  ON  TELLURIUM  333 

and  'that,  although  the  premises  are  true  and  give  cause  for  detrimental  conse 
quences,  you  were  unjustly  insulted. 

I  remain,  however,  with  best  regards,  Sir, 

Your  devoted  and  respectful  friend, 
K[itaibel]. 

Klaproth  replied  as  follows: 

Berlin,  Oct.  4,  1803. 

Highly  esteemed  Colleague: 

I  am  greatly  indebted  to  you  for  your  obligingly  prompt  reply  to  my  last 
letter.  I  must  confess,  however,  that  its  contents  by  no  means  fulfilled  my  ex 
pectations  as  completely  as  I  had  hoped.  In  the  meantime  I  ask  you  to  pardon 
me  if  I  am  wrong  [in  believing]  that  there  still  remains  in  your  mind  some  doubt 
as  to  the  truth  of  my  explanation:  that  the  article  which  Estner  communicated 
to  me  in  Vienna  has  not  had  the  slightest  influence  on  my  experiments  with 
tellurium.  Only  now  does  your  present  letter  recall  to  my  mind  that  I  have  been 
concerned  with  the  subject  of  molybdic  silver;  but,  as  regards  what  you  said 
about  it,  even  at  this  moment  I  remember  not  a  single  syllable,  and  I  all  the 
more  regret  that  you  did  not  publish  this  work  of  yours  long  ago.  I  boldly 
and  confidently  ask  all  my  friends,  here  and  abroad,  who  know  me  better,  if  it 
is  in  any  way  compatible  with  my  character  to  be  a  plagiarist  and  if  they  cannot 
attest  on  the  contrary  that  discoveries  which  belong  to  me  have  reached  the 
public  through  others,  without  my  being  able  to  claim  them.  Yes,  indeed. 
Even  today  I  would  rather  have  made  a  dozen  fewer  discoveries  than  to  bear 
for  a  moment  the  slightest  suspicion  that  I  could  seize  the  literary  property  of 

others. 

I  believe  I  have  already  mentioned  in  my  preceding  letter  that,  several 
years  before  my  trip  to  Vienna,  perhaps  in  1785  to  1786,  I  had  already  worked 
with  the  so-called  auro  problematic  which  the  late  Mr.  von  Fichtel  had  sent 
here  to  my  honored  friend,  Treasurer  Siegfried,  and  that  I  was  guided  by  the 
experiments  which  Mr.  Miiller  von  Reichenstein  had  made  and  had  described 
in  the  Physical  Researches,  and  whose  belief  that  it  contains  a  new  metal  I 
found  to  be  well  grounded;  to  which  conclusion  the  beautiful  criterion  previously 
announced  by  M.  v.  R.,  the  red  color  which  this  metal  imparts  to  sulfuric  acid, 
was  also  of  special  value.  Several  of  my  friends  here  and  members  of  my 
audience  at  that  time  can  and  will  testify  to  this. 

Now  just  what  have  I  done?  Nothing,  except  to  carry  out  a  few  little  ex 
periments  in  addition  to  those  published  by  Mr.  M.  v.  R.  on  the  ore  which  he 
himself  supplied.  But  I  must  almost  surmise  that  you  have  not  seen  my  com 
plete  paper  on  tellurium.  Otherwise  you  could  not  possibly  retain  the  error  that 
I ...  [have  claimed]  the  discovery.  Nowhere  have  I  said  that;  on  the  contrary, 
I  have  expressly  and  emphatically  explained  that  the  credit  for  the  discovery 
belongs  to  Mr.  Miiller  von  Reichenstein.  Can  one  more  definitely  observe  the 
suum  cuique?  Now  since  I  have  never  claimed  the  discovery,  it  is  now  as  clear 


334  DISCOVERY  OF  THE  ELEMENTS 

as  day  that  I  cannot  have  robbed  anyone  of  this  honor.  I  shall  now  leave  it  to 
you,  esteemed  colleague,  as  to  what  course  you  may  deem  best  to  give  complete 
satisfaction  as  soon  as  possible  for  my  publicly  insulted  honor  which,  to  this  day, 
suffers  blamelessly,  without  compelling  me  to  appear  in  my  own  defense;  for  I 
hate  scholastic  feuds  like  sin.  If  this  be  done  to  my  satisfaction,  as  I 
have  occasion  to  hope  that  it  will,  it  will  incomparably  increase  my  esteem  and 
respect  for  you  as  a  friend  and  colleague  whose  zeal  and  services  in  one  of  the 
most  beautiful  branches  of  natural  science  I  gladly  recognize  the  honor. 
With  highest  esteem,  I  remain,  Sir, 

Your  obedient  friend  and  colleague, 
(Signed)  Klaproth. 

Thoroughly  convinced  of  Klaproth's  integrity,  Kitaibel  promptly 
published  the  following  explanation  (10):  (Since  the  circumstances 
which  gave  rise  to  the  unjust  charge  against  Klaproth  were  stated  in 
detail  in  the  preceding  letters,  they  may  be  omitted  here). 

Pest,  Oct.  18,  1803. 

.  .  .  The  correct  conclusion  to  be  drawn  really  amounts  to  this:  that  I 
discovered  tellurium  in  a  misunderstood  and  hitherto  uncertain  ore  at  a  time 
when  the  individuality  of  this  metal  and  its  existence  in  the  Transylvanian  gold 
ores  had  not  been  publicly  confirmed  through  the  excellent  researches  of  Mr. 
Klaproth,  and  more  than  this  I  did  not  wish  to  claim  for  myself,  as  can  be  seen 
from  the  Zeitschrift  von  und  -fur  Ungarn,  volume  1,  page  275  ff.  For  Mr. 
Klaproth  has  himself  pointed  out  in  volume  3,  page  16  of  his  Beytrage  that 
the  credit  for  the  original  discovery  of  tellurium  belongs  to  Mr.  Miiller  von 
Reichenstein,  aulic  counselor  [Hofrath]. 

However,  further  inferences  have  been  made  and  conclusions  drawn  from 
the  aforementioned  circumstances  that  Mr.  Klaproth  had  borrowed  from  me 
the  'discovery  of  tellurium,  which  I  hereby  declare  on  the  following  grounds  to 
be  highly  unjust  and  false:  In  the  first  place,  Mr.  Klaproth's  blameless  character 
is  a  security  that  he,  who  had  no  need  for  such  a  despicable  means  of  increasing 
his  great  deserts  and  his  most  widespread  renown,  was  incapable  of  any  such 
action;  in  the  second  place,  his  researches  on  tellurium  and  tellurium  ores  are 
so  extensive  that  they  could  not  have  been  carried  out  so  completely  in  the  short 
time  in  which  they  appeared  after  his  departure  from  Vienna;  in  the  third  place, 
there  is  considerable  difference  between  Mr.  Klaproth's  researches  and  my  own, 
not  only  in  the  success  of  a  few  experiments,  but  also  in  the  completeness  of 
their  execution.  I  found,  for  example,  that  tellurium  is  precipitated  from  nitric 
acid  by  water  and  that  the  concentrated  sulfuric  acid  from  this  metal  becomes 
at  first  brown,  then  red,  and  finally,  after  continued  heating,  becomes  colorless 
again.  Mr.  Klaproth's  investigation,  on  the  contrary,  left  mine  far  behind  in 
completeness,  hence  the  two  cannot  be  compared;  finally,  Mr.  Klaproth  could 
certainly  not  borrow  from  me  a  discovery  which  belongs  neither  to  him  nor  to 


KLAPROTH-KITAIBEL  LETTERS  ON  TELLURIUM  335 

me  (NB.  For  [the  statement]:  "Mr.  Klaproth  has  himself  already  pointed  out 
in  volume  3,  page  16  of  his  Beytrage  that  the  credit  for  the  original  discovery  of 
tellurium  belongs  to  Mr.  Miiller  von  Reichenstein,  aulic  counselor"  has  been 
mentioned  here  on  page  461!),  as  Abbe  Eder*  has  so  correctly  observed  in  the 
Zeitschrift  von  und  fur  Ungarn,  volume  2,  page  90. 

Paul  Kitaibel,  Professor. 

Professor  Kitaibel's  love  for  botany  was  stimulated  by  his  oppor 
tunity  to  arrange  the  rich  herbarium  of  Counselor  Mygind,  a  friend  of 
Linne.  In  1793,  after  a  scientific  tour  of  Croatia,  he  returned  to  Pest  to 
join  the  staff  of  the  school  of  pharmacy.  After  managing  the  botanical 
garden  for  a  time,  he  became  a  professor  of  botany  and  chemistry,  giving 
no  lectures,  however,  but  spending  most  of  his  time  on  scientific  expedi 
tions.  In  1795  and  1796  he  studied  the  chalybeate  spring  at  Bardiov 
[Bartfeld,  or  Bartfa]  and  the  flora  of  the  Carpathians,  and  with  Count 
Franz  Adam  von  Waldstein  explored  the  territory  around  the  Sea  of 
Marmora.  On  a  visit  to  Berlin  he  met  K.  L.  Willdenow,  who  later  named 
a  genus  of  malvacese  Kitaibelia  in  his  honor.  He  also  explored  the 
beautiful  shores  of  Lake  Balaton  (the  Plattensee,  famous  for  its  delicious 
fish),  the  fertile  Banat,  and  most  of  Hungary. 

Kitaibel  published  a  number  of  books  and  articles  on  the  flora  and 
mineral  waters  of  Hungary,  and  according  to  Professor  L.  von  Szathmary 
(11),  was  the  first  to  prepare  solid  bleaching  powder  and  use  it  for 
bleaching  textiles. 

Unfortunately,  most  of  Kitaibel's  work  was  never  published,  but  his 
manuscripts  preserved  at  the  Hungarian  National  Museum  in  Budapest 
show  that  he  was  an  ingenious  designer  of  chemical  apparatus,  such  as 
a  salt-evaporating  pan  which  utilized  the  heat  of  the  fuel  gas  on  the 
counter  current  principle;  a  device  for  the  saturation  of  mineral  water 
with  carbon  dioxide;  apparatuses  for  vacuum  filtration  and  for  the  dis 
tillation  of  water;  and  an  improved  Hme  kiln  and  brick  kiln  (12). 

Kitaibel  died  at  Budapest  on  December  13,  1817,  at  the  age  of  sixty- 
three  years;  Klaproth's  life  had  come  to  a  close  on  New  Year's  Day  of  the 
same  year.  One  of  their  younger  contemporaries  wrote  for  the  botani 
cal  journal  Flora  a  memorial  article  entitled  "Some  Flowers  on  the  Grave 
of  Paul  Kitaibel"  (5),  in  which  appears  the  following  characterization: 
"Honest  and  outspoken,  expressing  his  opinion  openly  among  his  friends, 
and  brandishing  the  lash  of  the  satyrs,  he  disdained  (although  sought 
out  because  of  the  kindnes  of  his  disposition,  the  extent  of  his  knowledge, 
and  the  force  of  his  intellect)  all  vain  social  formalities.  .  .  ." 

Kitaibel's  valuable  library  was  purchased  by  the  National  Museum  of 
Budapest,  which  still  treasures  the  letters  which  have  here  been  cited. 

*  Joseph  Karl  Eder  (1760-1810).    Transylvanian  historian  and  mineralogist. 


336  DISCOVERY  OF  THE  ELEMENTS 

Although  this  intimate  correspondence  refers  to  a  disconcerting  and  em 
barrassing  situation  in  their  lives,  it  casts  no  shadow  on  the  reputation  of 
either  Klaproth  or  Kitaibel.  Their  names,  on  the  contrary  shine  all  the 
more  brightly  today  because  they  refrained  from  the  bitter  polemics 
of  the  printed  page  and  settled  their  serious  misunderstanding  through 
the  exchange  of  these  restrained  and  courteous  letters. 

The  author  is  deeply  indebted  to  Dr.  Max  Speter  of  Berlin  and  to  Dr. 
L.  von  Szathmary  of  Budapest  for  the  use  of  their  notes  and  of  the  Klap- 
roth-Kitaibel  correspondence,  for  their  many  gracious  and  helpful 
suggestions,  and  for  the  reading  of  the  manuscript;  and  to  Dr.  Frantisek 
Fiala,  Director  of  the  State  Museum  of  Mines  of  Stiavnica  Banska,  for 
his  kindness  in  sending  photographs  and  information  regarding  the 
former  School  of  Mines  of  Schemnitz.  It  is  also  a  pleasure  to  acknowl 
edge  the  assistance  received  from  the  Graduate  Research  Fund  of  the 
University  of  Kansas  for  translations  from  the  Hungarian,  which  were 
made  by  Mr.  Julius  Nagy  of  Chicago. 

LITERATURE  CITED 

( 1 )  SZATHMARY,  LASZLO,  "Paul  Kitaibel,  the  Hungarian  chemist,"  Magyar  Gyogys- 

zeresztud.  Tdrsasdg  Ertesitoje,  No.  4,  1—35  (1931);  "Concerning  the  polem 
ics  which  led  to  the  discovery  of  tellurium,"  ibid.,  No.  1,  1-11  ( 1932). 

(2)  MULLER,  F.  J.,  "t)ber  den  vermeintlichen  natiirlichen  Spiessglaskonig,"  Physi- 

kalische  Arbeiten  der  eintrachtigen  Freunde  in  Wien,  1  (1),  57—9  (1783). 

(3)  MULLER,  F.  J.,  "Versuch  mit  dem  in  der  Grube  Mariahilf  in  dem  Gebirge 

Facebaj  bei  Zalatna  vorkommenden  vermeinten  gediegenen  Spiessglaskonig," 
Physikalische  Arbeiten  der  eintrachtigen  Freunde  in  Wien,  I  ( 1 )  63-9 
(1783);  1  (2),  49-53  (1784);  1  (3),  34-52  (1785). 

(4)  VON  WALDSTEIN,  WALDAUF,  "Ueber  den  eigentlichen  Entdecker  des  Tellur- 

erzes,"  Vaterlandische  Blatter  fur  den  osterreichischen  Kaiserstaat,  1,  515—16 
(Oct.  3,  1818). 

(5)  SCHULTES,  "Einige  Blumen  auf  das  Grab  Paul  Kitaibel's,"  Flora,  14,  149-59 

(1831). 

(6)  VON  WOTZBACH,   C.,  "Biographisches  Lexikon  des  Kaiserthums  Oesterreich/' 

Vol.  11,  Kaiserlich-konigliche  Hof-  und  Staatsdruckerei,  1864,  pp.  337-9. 
This  lexicon  also  contains  biographical  sketches  of  Born,  Fichtel,  Haidinger, 
Muller  von  Reichenstein,  Piller,  Rupprecht,  Schedius,  and  Waldstein. 

( 7)  DOBLING,  H.,  "Die  Chemie  in  Jena  zur  Goethezeit,"  Gustav  Fischer,  Jena,  1928, 

220  pp. 

(8)  KLAPROTH,  M.  H.,  "Analytical  Essays  towards  Promoting  the  Chemical  Knowl 

edge  of  Mineral  Substances,"  Cadell  and  Davies,  London,  1801,  pp.  218-20. 
(Klaproth  found  no  silver  in  this  ore.) 

(9)  "Fortgesetzte  Nachrichten  liber  Ungarns  neueste  Literatur  und  Kultur,"  Der 

neue  deutsche  Merkur,  Stuck  4,  298-9  (1803). 

(10)  KITAIBEL,  P.,  "Erklarung,"  Gehlens  Allgem.  J.  der  Chemie,  1,  460-1  ( 1803). 

(11)  VON  SZATHMARY,  L.,  "Paul  Kitaibel  entdeckt  den  Chlorkalk,"  Chem.-Ztg,,  55, 

645  (Aug.  22,  1931);  ibid.,  55,  784  (Oct.  10,  1931).  "Kitaibel  felfedezi  a 
klormeszet,"  Kiilonlenyomat,  a  Termeszettudomanyi  Kozlony,  1930.  evi 
marc.  1-i  szamdbol. 


KXAPROTH-KITAIBEL  LETTERS  ON  TELLURIUM  337 

(12)  SZATHMARY,  L.  VON,  "Emige  chemisch-physikalische  Apparate  des  ungarischen 

Chemikers  Paul  Kitaibel  (1757-1817),"  Chem.  Apparatur,  19,  49-50  (Mar. 
10,1932). 

(13)  WURZBACH,  C.  VON,  Ref.  (6),  Vol.  2,  pp.  71-4.    Article  on  Ignaz  Edler  von 

Born. 

(14)  ZINCKE,  PAUL,  and  ALBERT  LEITZMANN,  "Georg  Forster's  Tagebiicher,"  B. 

Behr's  Verlag,  Berlin,  1914,  p.  147. 

(15)  BANCIU,  A.  S.,  Revista  de  Chimie,  10,  28-9  (Jan.  1959).     In  this  Roumanian 

article  on  the  history  of  tellurium  the  modern  geographical  names  are  given 
as  Ardeal  instead  of  Transylvania,  Sibiu  instead  of  Nagyszeben,  Fata  Baii  and 
Zlatna  instead  of  Facebaj  and  Salatna,  Sacarimb  instead  of  Nagyag,  Baia  de 
Aries  and  Metallic  Mountains  instead  of  Offenbanya  and  Borzsony  Moun 
tains,  Cluj  instead  of  Karlsburg.  In  Roumania  the  ore  nagyagite  is  called 
sacarimbit. 


Charles  Hatchett,  1765-1847. 

English  chemist  and  manufac 
turer.  Discoverer  of  niobium. 
Most  of  his  researches  were  in 
analytical  and  mineralogical 
chemistry. 


Edgar  Fahs  Smith  Memorial  Collection, 
University  of  Pennsylvania 


It  is  impossible  that  he  who  has  once  imbibed  a  taste 
for  science  can  ever  abandon  it  (1). 


13 


Niobium  (columbium).,  tantalum,  vanadium 

Although  the  metals  niobium,  tantalum,  and  vanadium  were 
recognized  very  early  in  the  nineteenth  century,  the  difficult  task 
of  preparing  them  in  a  pure  state  is  an  achievement  of  recent 
years.  In  1801  the  English  chemist  Charles  Hatchett  discovered 
a  new  element  e£columbium"  in  a  specimen  of  columbite  which 
had  an  interesting  connection  with  the  history  of  New  England. 
In  the  same  year  A.  M.  del  Rio,  a  professor  of  mineralogy  in 
Mexico,  examined  some  "brown  lead  from  Zimapdn"  and  an 
nounced  the  discovery  of  a  new  metal,  erythronium.  In  the 
following  year  Berzelius'  professor,  A.  G.  Ekeberg,  analyzed 
some  tantalite  from  Finland  and  found  in  it  an  element  very  simi 
lar  to  Hatchett's  columbium.  Although  Dr.  Wollaston  believed 
that  columbium  (niobium)  and  tantalum  are  identical,  Heinrich 
Rose  and  Marignac  proved  that  they  are  two  distinct  elements. 
In  1831  Sef strom  found  in  some  soft  iron  from  Eckersholm  a 
metal,  vanadium,  which  Wohler  proved  to  be  identical  with  del 
Rio's  erythronium. 

NIOBIUM 


he  element  columbium  (niobium)  was  discovered  in  1801 
by  the  English  chemist  Charles  Hatchett,*  who  was  born  in  London  in 
1765.  As  a  young  man  in  his  thirties  he  engaged  actively  in  chemical 
research,  and  published  in  titie  Philosophical  Transactions  an  analysis  of 
lead  molybdate  from  Carinthia  and  the  results  of  some  experiments  on 
shell  and  bone  (2),  and  in  Nicholsons  Journal  an  analysis  of  an  earth 
from  New  South  Wales  called  "Sydneia,  or  Terra  Australia"  (31). 

The  discovery  on  which  his  fame  rests  was  announced  before  the 
Royal  Society  on  November  26,  1801,  in  a  paper  entitled  "Analysis  of  a 
Mineral  from  North  America  containing  a  Metal  hitherto  Unknown"  (3). 
This  mineral,  now  known  as  columbite,  is  a  black  rock  found  in  New 
England,  and  the  specimen  Hatchett  analyzed  had  an  interesting  history. 

Governor  John  Winthrop  the  Younger  (SO,  46,  52)  used  to  take 
great  pleasure  in  examining  minerals,  and  his  manner  of  collecting  them 
is  best  described  in  the  quaint  words  of  an  early  American  poet: 

*  See  also  Chapter  14,  pp.  368-389. 

339 


340 


DISCOVERY  OF  THE  ELEMENTS 


John  Winthrop  the  Younger,  1606- 
1676.  First  governor  of  Connecticut. 
Alchemist,  manufacturing  chemist,  and 
physician.  His  grandson  sent  the  co- 
lumbite  from  which  Charles  Hatchett 
later  isolated  the  metal  columbium. 


From  Waters"  "A  Sketch  of  the  Life  of 
John  Winthrop  the  Younger" 

Sometimes  his  wary  steps,  but  toand'ring  too, 
Would  carry  him  the  Chrystal  Mountains  to, 
Where  Nature  locks  her  Gems,  each  costly  spark 
Mocking  the  Stars,  sphered  in  their  Cloisters  dark. 
Sometimes  the  Hough,  anon  the  Gardners  Spade 
He  deigned  to  use,  and  tools  of  th'  Chymick  trade  (47). 

On  one  of  these  expeditions  he  may  have  found  in  a  spring  near  his  home 
at  New  London,  Connecticut,  the  rock  fragment  of  columbite  which  his 
grandson  sent  to  Sir  Hans  Sloane  (1660-1753)  in  London  (4).* 

The  original,  historic  specimen  of  columbite  is  preserved  in  the 
British  Museum  (67).  A  portion  of  it  was  used  by  Charles  Hatchett  in 
1802  in  his  famous  research  which  culminated  in  the  discovery  of  colum 
bium.  In  1809  Dr.  W.  H.  Wollaston  obtained  permission  to  detach 
another  portion  of  it  for  an  investigation,  from  which  he  incorrectly  con 
cluded  that  columbium  and  tantalum  are  identical  (68). 

Since  columbite  is  a  very  complex  mineral  indeed,  containing 
niobic,  tantalic,  titanic,  and  tungstic  acids,  zirconia,  thoria,  ceria,  and 
yttria,  Hatchett  must  have  possessed  great  analytical  ability  in  order  to 
discover  in  it  the  new  element,  columbium.  Although  the  greatest  chem- 

*  See  also  Chapter  14,  pp.  371-380. 


NIOBIUM  (COLUMBIUM),  TANTALUM,  VANADIUM        341 


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Edgar  F.  Smith  Memorial  Collection,  University  of  Pennsylvania 

Autograph  Letter  of  Charles  Hatchett.  William  Thomas  Brande  (1788-1868), 
Davy's  successor  at  the  Royal  Institution,  was  Charles  Hatchett's  son-in-law. 
The  English  edition  of  Brande's  "Manual  of  Chemistry"  was  dedicated  to  Hatchett 

ists  in  Europe  held  for  more  than  forty  years  the  erroneous  opinion  that 
columbium  and  tantalum  are  identical,  Marignac  and  Heinrich  Rose 
finally  proved  that  they  are  two  distinct  elements.  Thus  Hatchett  was 
correct  in  concluding  that  he  had  found  a  new  metal  in  columbite  (53). 
A.-F.  de  Fourcroy  said  in  1799  that  the  most  industrious  chemist  in 
England  was  Charles  Hatchett,  whose  father,  the  King's  saddle-maker, 


342 


DISCOVERY  OF  THE  ELEMENTS 


had  offered  him  an  annual  income  of  3000  pounds  sterling  and  a  seat  in 
Parliament  if  he  would  renounce  this  science.  "Charles  Hatchett,"  said 
Fourcroy,  "preferred  the  study  of  chemistry,  and  found  the  means  to 
continue  its  cultivation.  The  analysis  of  minerals  is  what  occupies 
and  pleases  him  the  most;  he  is  very  clever  at  it;  one  can  rely  on  his  ex 
periments.  A  few  hours  of  work  in  his  laboratory  suffice  for  his  enjoyment 
and  instruction.  This  is  not,  by  any  means,  the  kind  of  continuous  re 
search  we  know  among  the  French  chemists'*  (69). 


Sir  Hans  Sloane,  1660- 
1753.  Founder  of  the 
British  Museum.  Physi 
cian,  pharmacist,  traveler, 
and  collector  of  books, 
manuscripts,  coins,  med 
als,  gems,  antiquities,  and 
natural  history  specimens. 
His  asbestos  specimens 
were  purchased  from 
Benjamin  Franklin  (63). 


It  is  to  be  regretted  that  a  man  of  such  great  ability  should  have 
given  up  his  scientific  research  early  in  life.  Thomas  Thomson  said  of 
him  in  1830,  ".  .  .  unfortunately  this  most  amiable  and  accomplished  man 
has  been  lost  to  science  for  more  than  a  quarter  of  a  century;  the  baneful 
effects  of  wealth,  and  the  cares  of  a  lucrative  and  extensive  business 
having  completely  weaned  him  from  scientific  pursuits"  (5).  In  1845 
Berzelius,  writing  to  Wohler,  expressed  a  similar  opinion:  "On  my 
previous  visit  here  in  Karlsbad,"  said  he,  "I  made  the  personal  acquain 
tance  of  your  king  as  Prince  of  Cumberland.  He  asked  me  if  I  knew 
a  number  of  English  chemists,  and  upon  my  replying  that  I  knew  Davy, 
Wollaston,  Tennant,  and  Marcet,  he  shook  his  head  and  indicated  that 


NIOBIUM  (COLUMBIUM),  TANTALUM,  VANADIUM        343 

I  had  forgotten  the  foremost  one,  namely,  Hatchett  He  seemed  greatly 
pleased  that  I  also  knew  him,  however  did  not  want  to  believe  that  he 
had  given  up  chemistry  and  become  a  coach-maker  as  his  father's 
successor"  (6).  Hatchett  retired  to  his  estate  at  Roehampton,  near 
London,  and  died  at  Chelsea  on  March  10,  1847. 

He  never  succeeded  in  isolating  niobium,  and  in  fact  the  element 
eluded  chemists  for  more  than  six  decades.  In  1864,  however,  C.  W. 
Blomstrand  reduced  niobium  chloride  by  heating  it  strongly  in  an  at 
mosphere  of  hydrogen  (48),  and  saw  the  shining  steel-gray  metal. 


Henri  Moissan,  1852-1907.  Professor  of 
Chemistry  at  the  Ecole  de  Pharmacie,  and 
at  the  Sorbonne.  The  first  to  isolate 
fluorine  and  make  a  thorough  study  of  its 
properties.  With  his  electric  furnace  he 
prepared  artificial  diamonds  and  many 
rare  metals.  He  brought  about  a  revival 
of  interest  in  inorganic  chemical  research. 


In  1901  Henri  Moissan  pulverized  some  American  columbite,  mixed 
with  it  some  sugar  charcoal,  compressed  the  mixture,  and  heated  it  from 
seven  to  eight  minutes  in  his  electric  furnace,  using  a  current  of  one 
thousand  amperes  under  fifty  volts.  After  volatilizing  all  the  manganese 
and  part  of  the  iron  and  silicon,  he  obtained  a  melt  containing  niobium 
and  tantalum  combined  with  carbon. 

After  preparing  niobic  acid  by  Marignac's  method,  he  mixed  eighty- 
two  parts  of  it  with  eighteen  of  sugar  carbon,  moistened  the  mixture 
slightly  with  turpentine,  and  pressed  it  into  the  form  of  a  cylinder,  which 
he  heated  in  his  electric  furnace,  using  six  hundred  amperes  under  fifty 
volts.  A  violent  reaction  took  place  in  accordance  with  the  equation: 

Nb205  +  5C  =  2Nb  +  SCO. 
After  cooling  the  mixture  out  of  contact  with  the  nitrogen  of  the 


344 


DISCOVERY  OF  THE  ELEMENTS 


air,  he  found  a  well-fused  ingot  with  a  metallic  fracture  (49).  Moissan's 
niobium  contained  a  small  amount  of  combined  carbon,  and  was  so 
inert  and  refractory  that  he  believed  the  element  to  be  a  non-metal 
resembling  boron  and  silicon. 

From  1904  to  1910  d  W.  Balke  (7,  IS,  55)  analyzed  many  niobium 
and  tantalum  compounds  and  determined  the  atomic  weights  of  both 
metals.  In  1906  Werner  von  Bolton  of  the  Siemens  &  Halske  Company 


Courtesy  Fansteel  Products  Company,  Inc. 
Photomicrograph  of  Niobium.     Approximately  300  X- 


prepared  a  niobium  regulus  by  an  alummo-thermic  method  and  purified 
it  by  repeated  melting  in  a  vacuum  electric  furnace  (17,18).  For  twenty- 
three  years  this  little  specimen  in  Germany  continued  to  be  the  only  piece 
of  pure  niobium  in  the  world,  but  in  May,  1929,  Dr.  Balke  exhibited 
before  the  American  Chemical  Society  some  highly  polished  sheets  and 


NIOBIUM  (COLUMBIUM),  TANTALUM,  VANADIUM        345 

rods  of  this  rare  metal.  Because  less  energy  is  required  to  remove  an 
electron  from  its  surface  than  from  that  of  any  other  refractory  metal, 
niobium  is  used  in  vacuum  tubes  for  high-power  service  ( 56' ) . 

TANTALUM 

Since  minerals  which  contain  niobium  almost  invariably  contain  also 
the  closely  related  element,  tantalum,  it  is  small  wonder  that  chemists 
at  first  confused  the  two  elements.  The  discoverer  of  tantalum  was  the 
Swedish  chemist  and  mineralogist  Anders  Gustaf  Ekeberg.  He  was  born 
at  Stockholm  on  January  16,  1767,  the  son  of  Joseph  Erik  Ekeberg,  a 


Anders      Gustaf     Ekeberg,     1767-1813. 

Swedish  chemist,  mineralogist,  poet,  and 
artist.  Professor  of  Chemistry  at  Upsala 
when  Berzelius  was  a  student  there.  The 
discoverer  of  tantalum.  He  was  one  of 
the  first  chemists  to  investigate  yttria. 


shipbuilder  in  the  service  of  the  King.  When  he  was  ten  years  old  he 
was  sent  to  school  at  Kalmar,  and  two  years  later  he  went  to  Soderakra 
where  he  boarded  at  the  home  of  the  clergyman.  It  was  there  that  he 
gained  his  first  knowledge  of  Greek  literature,  a  subject  which  gave  him 
great  pleasure  throughout  his  life.  When  he  was  fourteen  years  old,  he 
attended  school  at  Vestervik  and  at  Carlscrona  and  was  an  apt  scholar 
both  in  science  and  in  art. 

He  graduated  from  the  University  of  Upsala  in  1788,  presenting  a 
thesis  on  Oils  Extracted  from  Seeds,  and  traveled,  on  salary,  through 
Germany.  Soon  after  his  return  to  Upsala  in  1790  he  wrote  a  beautiful 
poem  on  the  peace  recently  concluded  between  Sweden  and  Russia. 


346  DISCOVERY  OF  THE  ELEMENTS 

In  1794,  after  publishing  his  first  contribution  to  chemistry,  he  began 
his  teaching  career  at  Upsala  where  he  soon  distinguished  himself  as 
an  analytical  chemist  and  proponent  of  Lavoisier's  new  system  of  chemical 
nomenclature  (64).  In  1795  he  published  with  Pehr  Afzelius  a  bro 
chure  in  which  modern  names  for  such  elements  as  hydrogen,  nitrogen, 
and  oxygen  were  introduced  for  the  first  time  into  the  Swedish  language. 
When  Berzelius  was  studying  medicine  at  the  University  of  Upsala 
(1796-1802)  Ekeberg,  who  in  the  opinion  of  Anton  Blanck  was  at  that 
time  Sweden's  foremost  chemist,  was  serving  as  demonstrator  in  Torbern 
Bergman's  old  laboratory.  In  the  autumn  of  1798  Ekeberg  gave  lectures 
on  the  theory  of  combustion.  For  the  Litteratur  Tidning  published  at 
the  University  of  Upsala  he  wrote  excellent  articles  on  "The  present  state 
of  chemical  science"  and  on  "The  advantages  which  medicine  gains  from 
the  most  recent  discoveries  in  chemistry"  (64). 

Ekeberg  suffered  throughout  his  life  from  physical  handicaps. 
A  severe  cold  in  childhood  made  him  partially  deaf  for  the  rest  of  his 
life,  and  in  1801,  when  a  flask  exploded  in  his  hand,  he  lost  the  sight  of 
one  eye  (9). 

When  the  royal  family  visited  Upsala  in  November  of  that  year,  an 
elaborate  chemical  exposition  was  held  in  their  honor.  A  poem  of  three 
stanzas,  which  Ekeberg  had  composed  and  written  with  invisible  ink,  ap 
peared  in  blue  letters  when  the  King  warmed  the  paper.  It  began  as 
follows : 

That  in  our  land  the  sciences  pure  light 

Is  mingled  not  with  -flash  and  gleam  of  sword, 

Oh  Monarch,  'tis  thy  work.    Accept  our  hearts  oblation. 

May  we,  too,  celebrate,  with  joyous  visages. 

The  long-awaited  hour  when  Peace  the  world  doth  greet  (57).* 

Ekeberg  became  deeply  interested  in  the  wonderful  minerals  to  be 
found  at  Ytterby  and  Falun,  and  made  excellent  analyses  of  a  number 
of  them.  In  1802  he  analyzed  a  specimen  of  tantalite  from  Kimito,  Fin 
land,  and  another  mineral,  yttrotantalite,  from  Ytterby.  The  specimen  of 
tantalite  was  presented  to  him  by  Geyer,  Director  'of  Mines,  who  had 
discovered  it  in  1746  and  regarded  it  as  a  problematical  variety  of  tin 
garnet  (Zinngraupen).  Director  Geyer  found  it  near  the  Brokarn  estate 
at  Kimito,  Abo,  Finland,  on  a  mountain  on  the  shore  of  the  Baltic.  Mine 
surveyor  Nils  Nordenskiold  afterward  described  this  locality  as  follows: 
"Near  the  Skoybole  estate,  three  quarters  of  a  mile  from  the  Kimito 

*  At  Wetenskapers  rena  Dag 

Ej  blandades  hos  oss  med  blixtarne  af  swarden, 

Det  dr  ditt  werk,  Monark,  v&rt  hjertas  offer  tag! 

Wi  fire,  jemw'dl  wi,  med  gl'ddjens  anletsdrag 

Dem  lange  drogda  stund,  da  Freden  halsar  werlden. 


NIOBIUM    (COLUMBIUM),  TANTALUM,   VANADIUM  347 

church,  there  are  two  prospectors'  openings  which,  according  to  the 
statements  of  older  Finnish  mineralogists,  bear  a  kind  of  irregular 
stanniferous  garnet;  hence  the  locality  also  has  retained  the  name  tin- 
mine  of  Kimito. 

"The  openings,"  said  Nordenskiold,  "are  rather  old  and  are  said  to 
have  been  first  begun  on  the  word  of  a  rod-bearer  [who  said]  that  toward 
the  east  it  would  yield  silver.  Afterward,  the  spherical  mica  and  tan- 
talite  which  occur  there  attracted  the  notice  of  mineralogists.  The  open 
ings  lie  about  half  a  mile  from  the  manor,  back  in  the  forest,  in  a  swampy 
region,  on  a  low  mountain.  They  are  cut  into  an  east-west  stratum,  con 
sisting  of  a  matrix  of  mica,  red  albite,  and  quartz.  .  .  .  The  tantalite 


Heinrich  Rose,  1795-1864.  German  ana 
lytical  chemist  arid  pharmacist.  Son  of 
Valentin  Rose  the  Younger.  His  com 
parative  study  of  American  columbite  and 
Bavarian  tantalite  proved  that  columbium 
(niobium)  and  tantalum  are  two  distinct 
metals. 


formerly  existed  at  the  surface  in  greater  quantities,  but  has  now  so  far 
disappeared  that  tantalite  at  this  locality  may  correctly  be  considered  one 
of  the  rarest  of  fossils"  (70). 

Ekeberg  found  the  yttrotantalite  in  the  same  place  as  the  gadolinite 
at  Ytterby,  Sweden.  He  found  that  both  contained  a  hitherto  unknown 
metal.  Because  it  had  been  such  a  tantalizing  task  to  trace  it  down,  Eke 
berg  named  it  tantalum  (32). 

In  1809  Dr.  WoUaston  analyzed  both  columbite  and  tantalite  (10). 
His  conclusion  that  niobium  and  tantalum  are  identical  was  accepted  by 
chemists  until  1846,  when  Heinrich  Rose  (a  grandson  of  Valentin  Rose 
the  Elder  and  son  of  the  Rose  whom  Klaproth  educated )  questioned  it. 
Rose  had  made  a  thorough  study  of  the  columbites  and  tantalites  from 
America  and  from  Bodenmais,  Bavaria,  and  had  extracted  from  them 


348 


DISCOVERY  OF  THE  ELEMENTS 


two  acids  which  he  called  niobic  (columbic)  and  pelopic  acids.  He 
found  later,  however,  that  the  latter  was  not  the  acid  of  a  new  metal,  as 
he  had  at  first  supposed,  but  that  it  contained  niobium  (columbium)  in 
a  lower  state  of  oxidation.  Rose  stated  that  niobic  and  hyponiobic  acids 
are  both  different  from  tantalic  acid  (11). 


Thomas  Thomson,  1773-1852.  Scottish  chem 
ist  and  editor.  The  first  distinguished  advocate 
of  Dalton's  atomic  theory.  Author  of  a  two- 
volume  "History  of  Chemistry"  characterized  by 
its  scientific  accuracy  and  beautiful  literary 
style  (59,  60). 


Although  niobic  and  tantalic  acids  are  extremely  difficult  to  separate, 
Marignac  finally  succeeded,  not  only  in  separating  them,  but  also  in  show 
ing  that  niobium  is  both  tri-  and  pentavalent,  whereas  tantalum  always 
has  a  valence  of  five.  The  separation  is  based  on  the  insolubility  of 
potassium  fluotantalate  in  comparison  with  potassium  fluo-oxyniobate 
(12,  20).  In  the  United  States  the  element  discovered  by  Hatchett  used 
to  be  known  as  columbium,  but  in  Europe  most  chemists  prefer  to  use 
the  name  niobium  which  Heinrich  Rose  gave  it. 

Ekeberg's  later  years  were  made  less  fruitful  by  continued  illness. 


NIOBIUM  (COLUMBIUM),  TANTALUM,  VANADIUM        349 

The  few  papers  which  he  published  contained  the  results  of  the  analyses 
of  minerals  such  as  gadolinite,  the  topaz,  and  an  ore  of  titanium.  In  his 
analysis  of  the  mineral  water  of  Medevi  he  was  assisted  by  an  obscure 
young  student  who  was  destined  to  bring  great  glory  to-  the  University  of 
Upsala.  The  discovery  of  such  a  student  as  BerzeHus  was  a  far  greater 
honor  for  Ekeberg  than  his  disclosure  of  the  rather  rare  element, 
tantalum. 

BerzeHus  warmly  defended  Ekeberg's  claim  to  the  discovery  of 
this  element.  In  the  autumn  of  1814  he  wrote  to  Thomas  Thomson  ob 
jecting  to  an  alteration  which  had  been  made  in  an  English  translation  of 
one  of  his  memoirs.  BerzeHus  had  used  the  word  tantalum,  and  Thomson 
had  evidently  substituted  the  word  columbium,  whereupon  BerzeHus 
wrote,  "Without  wishing  to  depreciate  the  merits  of  the  celebrated 
Hatchett,  it  is  nevertheless  necessary  to  observe  that  tantalum  and  its 
properties  in  the  metallic  as  well  as  in  its  oxidized  condition  were  not 
known  at  all  before  Mr.  Ekeberg." 

BerzeHus  went  on  to  explain  the  differences  between  Ekeberg's 
tantalum  oxide  and  the  columbium  oxide  prepared  by  Hatchett: 

Mr.  Ekeberg  received  from  a  friend  who  had  visited  England  [said  he],  a 
little  portion  of  the  columbic  acid  of  Mr.  Hatchett,  and  when  the  experiments 
of  Mr.  Wollaston  came  to  his  knowledge  he  examined  that  acid  in  a  scrupulous 
manner.  He  recognized  in  it  a  large  amount  of  tungstic  acid  which  had  given  to 
the  oxide  its  properties  of  reacting  acid  as  well  as  those  of  combining  with  the 
alkaHes  and  of  coloring  microcosmic  salt.  These  observations  of  Mr.  Ekeberg 
have  gained  still  more  weight  by  the  discovery  of  a  new  fossil*  that  Mr.  Gahn 
and  I  have  just  made  near  Falun,  which  fossil  possesses  the  general  proper 
ties  of  Mr.  Hatchetfs  columbite,  and  in  the  analysis  of  which  we  have  found 
oxide  of  tantalum  combined  with  tungstic  acid.  .  ,  . 

Now,  then  [continued  Berzelius],  it  is  clear  that  the  columbic  acid  of  Mr. 
Hatchett,  having  been  composed  of  oxide  of  tantalum  and  tungstic  acid,  which 
communicated  to  it  a  part  of  its  specific  properties,  it  is  clear,  I  say,  that  Mr. 
Hatchett  shares  the  discovery  of  tantalum  in  almost  the  same  manner  as  MM. 
Fourcroy  and  VauqueHn  share  with  Mr.  Tennant  the  honor  of  having  discovered 
osmium  ("Thomson's  System,"  Ed.  IV,  Vol.  1,  p.  200),  and  I  suppose  that  you 
will  not  refuse  to  render  the  same  justice  to  the  work  of  trie  Swede  Ekeberg 
that  you  have  just  rendered  to  the  Englishman  Tennant.? 

As  for  the  name  of  the  metal  [said  Berzeliusl,  I  do  not  think  that  the  author 
of  the  discovery  ought  to  count  for  much.  For  example  you  do  not  say  menac- 
canite  instead  of  titanium;*  moreover  Mr.  Hatchett  gave  this  name  after  the 
place  where  it  was  thought  the  fossil  had  been  found;  now  it  is  not  good  practice 

*  A  tantaHte  from  Broddbo. 
f  See  Chapter  16,  p.  436-440. 
t  See  Chapter  21,  pp.  545-51. 


350  DISCOVERY  OF  THE  ELEMENTS 

to  name  elementary  substances  in  chemistry  after  the  places  where  they  have 
first  been  found;  not  to  mention  the  fact  that  the  place  where  columbite  was 
found  is  still  doubtful,  in  the  same  degree  as  it  is  not  certain  that  it  comes  from 
America.  The  name  tantalum  having  none  of  these  inconveniences  and  involv 
ing  a  beautiful  meaning  of  a  few  properties  of  this  particular  metallic  body,  I 
have  felt  compelled  to  choose  it  by  preference.  The  reason  for  the  name  tan 
talum  (derived  from  the  story  of  Tantalus)  is  still  more  valid  if  one  adds  that 
metallic  tantalum,  reduced  to  the  finest  powder,  is  not  attacked  by  any  acid, 
not  even  by  aqua  regia,  concentrated  and  boiling  (13) . 

In  his  reply  to  this  letter  on  November  5,  Thomson  explained  that 
he  had  known  very  little  about  Ekeberg's  experiments  and  that  his  only 
reason  for  changing  Berzelius'  nomenclature  had  been  to  make  the 
article  more  intelligible  to  English  readers.  He  then  added: 

I  regret  that  it  never  has  been  in  my  power  to  make  experiments  on  either 
of  these  substances  (columbite  or  tantalite) .  Ekeberg  supplied  me  with  a  good 
many  specimens,  but  the  ship  containing  them  and  all  my  Swedish  collection, 
which  I  valued  highly,  was  sunk  in  the  Baltic,  and  all  my  property  lost.  Your 
fact  about  the  new  mineral  like  columbite  [sic]  is  very  interesting.  I  shall  insert 
what  you  have  told  me  in  the  next  number  of  my  journal.  It  is  all  unknown 
here  (14). 

On  March  29,  1815  Dr.  Marcet  wrote  to  Berzelius: 

.  .  .  Dr.  Wollaston  made  some  time  ago  in  my  presence  a  little  experi 
mental  inquiry  on  wolfram  and  tantalite  and  columbite,  by  which  it  appeared 
that  Hatchetfs  columbite  did  not  contain  any  tungsten,  and  that  therefore  he 
did  not  make  the  mistake  you  suspected  he  had  made.  If  you  are  curious  to 
have  the  details,  I  shall  send  them  to  you  (15) . 

The  biographical  sketch  in  Vetenskapsacademiens  Handlingar  pic 
tures  Professor  Ekeberg  as  a  man  of  slender  build,  afflicted  with  tuber 
culosis,  deafness,  and  partial  blindness  which  had  resulted  from  a  labo 
ratory-  explosion.  "With  a  naturally  animated  and  energetic  temperament 
he  combined  a  charming  benevolence  which  spread  over  his  countenance 
and,  together  with  the  lines  of  suffering  so  evident  in  his  later  years, 
awakened  tender  sympathy  and  concern.  His  manner  inspired  confi 
dence.  He  was  a  gifted  teacher  and  devoted  friend"  ( 71 ) . 

Ekeberg  died  at  Upsala  on  February  11,  1813,  at  the  early  age  of 
forty-six  years.  In  a  letter  to  Dr.  Marcet  (16),  Berzelius  paid  the  follow 
ing  tribute  to  his  gifted  teacher:  "Ekeberg  has  just  died  after  a  long,  sad, 
hectic  illness.  He  was  one  of  the  most  lovable  of  men,  he  had  sound 
knowledge,  and  an  irresistible  propensity  for  work.  He  was  a  good 
chemist  and  mineralogist,  a  good  poet  and  an  excellent  artist."*  Ekeberg 

*  "Ekeberg  vient  de  mourir  apres  une  maladie  hectique  longue  et  malheureuse.  Get 
homme  etait  des  plus  aimables;  il  possedait  des  connaissances  solides  et  un  penchant 
irresistible  pour  le  travail.  II  etait  bon  chimiste  et  miner  alogue,,  heureux  poete  et 
tres  bon  peintre." 


NIOBIUM  (COLUMBIUM),  TANTALUM,  VANADIUM        351 

had  a  kind,  friendly,  merry  spirit  that  frequently  soared  above  poverty 
and  suffering,  and  his  love  of  literature  and  art  was  a  constant  solace  to 
him. 

Tantalum  can  be  separated  from  niobium  by  recrystallization  of  the 
double  potassium  fluorides.  In  the  commercial  process  the  ore  is  fused 
with  caustic  soda.  The  insoluble  sodium  niobate,  sodium  tantalate,  and 


Laboratory  Equipment 
Made  from  Tantalum 

Courtesy     Fansteel     Products 
Company,  Inc. 


iron  tantalate  are  filtered  off  from  the  soluble  sodium  salts,  and  the  iron 
is  removed  by  treatment  with  hydrochloric  acid.  The  niobic  and  tantalic 
acids  are  treated  with  hydrofluoric  acid  and  enough  potassium  fluoride 
to  convert  the  tantalum  into  the  double  fluoride,  K2TaF7?  which  is  then 
recrystallized  from  water  containing  a  little  hydrofluoric  acid  (7). 

After  Werner  von  Bolton  of  Charlottenburg  succeeded  in  1903  in 
refining  the  metal,  it  soon  acquired  a  limited  use  as  filaments  (34).  It 
was  found,  moreover,  that  surgical  and  dental  instruments  made  from 
it  can  be  sterilized  by  heating  or  by  immersion  in  acids  without  damage 
to  the  tantalum.  Since  the  price  was  almost  prohibitive,  however,  Dr. 
Balke  set  to  work  in  Chicago  to  make  the  metal  on  a  commercial  scale. 


Tantalum  for  Watch  Cases 

Courtesy  Fansteel  Products  Company,  Inc. 


Using  as  his  raw  material  a  rich  tantalum  ore  from  the  desolate  Pilbarra 
region  of  western  Australia,  he  finally  succeeded  in  February,  1922,  in 
preparing  a  tantalum  ingot  which  was  passed  repeatedly  through  a  rolling 
mill  to  produce  a  flawless  piece  of  sheet  metal  (8,  19). 

Tantalum  is  now  made  into  spinnerets  for  the  manufacture  of  rayon, 
into  electrodes  for  the  neon  signs  that  give  our  Great  White  Ways  a 


352 


DISCOVERY  OF  THE  ELEMENTS 


ruddier  light,  and  into  fine  jewelry  with  iridescent  colors.  Its  most 
interesting  use,  however,  depends  on  its  peculiar  electrochemical  be 
havior  caused  by  the  insolubility  of  its  oxide  in  acid  solution.  When  an 
alternating  current  is  passed  through  a  vessel  containing  sulfuric  acid, 
a  bar  of  lead,  and  a  bar  of  tantalum  (or  of  niobium),  it  becomes  a  direct 
current  (7,  19).  Thus,  because  direct  current  was  needed  in  the  early 


Sef Strom's  Autograph  on  title  page  of 
Berzelius'  treatise  on  the  blowpipe. 


days  of  radio  reception,  Ekeberg's  tantalizing  metal,  in  the  form  of  radio 
rectifiers,  "B"  battery  eliminators,  and  trickle  chargers,  entered  into 
the  home  life  of  thousands  upon  thousands  of  families.  It  has  also  been 
used  successfully  for  the  manufacture  of  standard  analytical  weights  (62). 


VANADIUM 

In  1801,  the  year  in  which  Hatchett  discovered  niobium,  Andres 
Manuel  del  Rio,  a  professor  of  mineralogy  in  Mexico,  examined  a  speci 
men  of  brown  lead  ore  from  Zimapan  and  concluded  that  it  contained  a 
metal  similar  to  chromium  and  uranium.  Little  has  been  written  concern 
ing  the  personal  life  of  del  Rio.*  He  was  born  in  Madrid  on  November 

*  See  Chapter  15,  pp.  390-405. 


NIOBIUM    (COLUMBIUM),  TANTALUM,   VANADIUM  353 


10,  1764,  studied  at  Freiberg  and  at  Schemnitz,  and  finally  became  a  pro 
fessor  in  the  School  of  Mines  (Colegio  de  Mineria)  in  Mexico  City,  where 
he  taught  for  more  than  fifty  years  (  1795-1849  )  (  2,  50,  51  )  . 

It  was  there  that  he  discovered  a  new  metal  which,  because  of  the 
red  color  that  its  salts  acquire  when  heated,  he  named  erythronium  (44). 
Upon  further  study,  however,  he  decided  that  he  was  mistaken,  and  that 
the  brown  lead  ore  from  Zimapan  was  a  basic  lead  chromate  con 
taining  80.72  per  cent  of  lead  oxide  and  14.80  per  cent  of  chromic  acid 
(12).  His  paper  therefore  bore  the  modest  title,  "Discovery  of  chromium 
in  the  brown  lead  of  Zimapan"  (21).  In  1805  Collet-Descotils  confirmed 
del  Rio's  analysis  (22),  and  for  twenty-five  years  no  more  was  heard  of 
the  new  element,  erythronium. 

In  his  textbook  of  mineralogy  published  in  Philadelphia  in  1832, 
however,  del  Rio  said  that  "the  metal  in  the  brown  lead  is  not  chromium 
but  vanadium,  the  very  same  (el  mismo  mismisimo)  which  I  called 
pancromo  and  eritrono  on  page  61  of  my  translation  [of  TCarsten's  Tables, 
Mexico/  1804]"  (72). 

In  1820  del  Rfo  went  to  the  Spanish  court  to  plead  for  Mexican  inde 
pendence.  His  paper  (I  )  on  the  "Analysis  of  an  alloy  of  gold  and  rhodium 
from  the  parting  house  at  Mexico"  was  published  in  the  Annals  of  Phi 
losophy  in  October,  1825.  The  closing  years  of  his  long  useful  life  were 
spent  in  Mexico,  where  he  died  on  March  23,  1849. 

In  1831  the  Swedish  chemist  Nils  Gabriel  Sefstrom  discovered  a  new 
element  in  iron  from  the  Taberg  mine  in  Smaland.  Sefstrom  was  born 
on  June  2,  1787,  at  Ilsbo  Socken,  Norra  Helsingland  (2).  He  studied 
medicine,  and  received  his  medical  degree  at  the  age  of  twenty-six  years. 
After  four  years  of  practice  in  a  hospital,  he  became  a  professor  of 
chemistry  and  science  at  the  Caroline  Institute  of  Medicine  and  Surgery, 
and  from  1820  to  1839  he  taught  chemistry  at  the  newly  erected  School 
of  Mines  at  Falun  (2,  54). 

It  was  there  that  he  made  the  remarkable  discovery  that  Berzelius 
described  so  charmingly  to  Wohler  in  his  letter  of  January  22,  1831: 

In  regard  to  the  sample  which  I  am  sending  with  this,  I  want  to  tell  the 
following  anecdote:  In  the  far  north  there  lived  in  olden  times  the  goddess 
Vanadis,  beautiful  and  lovable.  One  day  some  one  knocked  at  her  door.  The 
goddess  remained  comfortably  seated  and  thought:  let  the  person  knock  again; 
but  there  was  no  more  knocking,  and  the  one  who  had  knocked  went  down  the 
steps.  The  goddess  was  curious  to  see  who  it  might  be  that  was  so  indifferent 
to  being  admitted,  sprang  to  the  window,  and  looked  at  the  one  who  was  going 
away.  Alas!  she  said  to  herself,  that's  that  fellow  Wohler.  Well,  he  surely 
deserved  it;  if  he  had  been  a  little  more  concerned  about  it,  he  would  have  been 
admitted.  The  feUow  does  not  look  up  to  the  window  once  in  passing  by.  ... 


354 


DISCOVERY  OF  THE  ELEMENTS 


After  a  few  days  some  one  knocked  again  at  the  door;  but  this  time  the 
knocking  continued.  The  goddess  finally  came  herself  and  opened  the  door. 
Sefstrom  entered,  and  from  this  union  vanadium  was  born.  That  is  the  name 
of  the  new  metal,  whose  former  name  suggesting  Erian,  meaning  wool  (whence 
Erianae  was  educated,  since  Minerva  taught  human  beings  to  spin  wool),  has 
been  rejected.  The  Herr  Professor  guessed  correctly  that  the  lead  mineral  from 
Zimapan  contains  vanadium  and  not  chromium.  Sefstrom  himself  proved  with 
the  little  specimen  belonging  to  the  professor  that  it  is  vanadium  oxide. 


Nils  Gabriel  Sefstrom,  1787-1845.  Swe 
dish  physician  and  chemist.  Professor  at 
the  Caroline  Institute  of  Medicine  and 
Surgery  and  at  the  School  of  Mines  in 
Stockholm.  In  1831  he  discovered  vana 
dium,  an  element  that  proved  to  be 
identical  with  del  Rio's  "erythronium." 


Vanadium  [continued  Berzelius]  is  a  thing  which  is  very  hard  to  find.  It 
is  related  to  everything  with  which  it  forms  compounds  in  definite  proportions, 
even  to  silica,  so  that  only  now  have  I  been  able  to  obtain  it  pure.  In  Sef- 
strom's  vanadium  oxide  which  he  brought  with  him  are  found  phosphoric  acid, 
silica,  alumina,  zirconia,  and  ferric  oxide,  of  whose  presence  we  had  no  suspi 
cion,  but  which  we,  because  of  ambiguous  results,  had  to  remove,  one  after 
another;  so  that  in  the  three  weeks  which  Sefstrom  spent  in  working  with  me, 
we  confined  ourselves  almost  entirely  to  the  task  of  finding  these  impurities 
and  of  thinking  out  ways  of  removing  them.  Sefstrom  had  to  go  home,  but 
left  me  so  much  vanadium  that  I  have  been  in  no  embarrassment  over  the 
continuance  of  the  investigation,  I  shall  send  the  Herr  Professor  some  of  it 
later,  when  I  see  about  how  much  I  can  spare;  but  now  in  the  midst  of  the 
research  I  need  all  I  have  (23). 

Berzelius  then  consoled  Wohler  for  his  failure  to  discover  vanadium, 
saying  it  required  more  genius  to  synthesize  urea  than  to  discover  ten 


NIOBIUM  (COLUMBIUM),  TANTALUM,  VANADIUM        355 

new  elements  (58,  61).  <CI  have  mailed  to  Poggendorff,"  he  continued, 
"a  little  paper  on  vanadium  by  Sefstrom.  I  have  also  engaged  Sefstrom 
to  present  it  to  the  Academy  so  that  his  name  alone  may  be  linked  with 
the  discovery,  which  would  not  be  the  case  if  the  first  paper  on  it  ap 
peared  under  his  and  my  name  together.  Thus  it  also  becomes  possible 
to  announce  the  discovery  sooner  than  if  we  had  to  wait  for  the  con 
clusion  of  my  research,  which  surely  connot  be  completed  so  quickly" 


Two  weeks  later  Wohler  replied: 

A  thousand  thanks,  dear  professor,  for  your  kind  letter  with  the  beautiful 
story  about  the  goddess  Vanadis,  which  gave  me  great  pleasure,  although, 
frankly,  it  vexed  me  a  little,  though  only  at  first,  to  have  made  no  visit  to  the 
beautiful  one.  Even  if  I  had  charmed  her  out  of  the  lead  mineral,  I  would  have 
had  only  half  the  honor  of  discovery,  because  of  the  earlier  results  of  del  Rio 
on  erythronium.  But  Sefstrom,  because  lie  succeeded  by  an  entirely  different 
method,  keeps  the  honor  unshared.  As  soon  as  I  know  the  intimate  relations 
of  the  metal,  and  you  have  sent  me  a  little  of  it,  I  will  analyze  the  lead  min 
eral.  .  .  . 

Anticipatory  as  it  may  seem  [continued  Wohler]  yet,  because  of  the  slow 
ness  of  the  mails,  it  is  time  to  ask  whether,  when  I  publish  a  notice  of  the  min 
eral,  I  ought  to  give  its  earlier  history,  the  supposed  discovery  by  del  Rio  of  a 
new  metal  in  it,  the  refutation  -by  Descotils?  that  Humboldt  brought  it  with  him, 
etc.?  I  would  not  want  in  the  least  to  take  away  from  Sefstrom  anything  of  his 
priority  of  discovery,  especially  since  such  indecision  is  repugnant  in  cases  like 
this;  on  the  other  hand  one  must  not  expose  one's  self  to  the  charge  by  the  public 
or  especially  by  one's  opponents  that  one  through  partisanship  concealed 
earlier  claims.  In  any  case  Humboldt  shall  be  named,  since  he  alone  brought  it 
with  him,  and  with  that  the  rest  seems  unavoidably  linked.  Do  not  laugh  at 
me  because  of  my  diplomatic  question  .  .  .  (23) . 

The  keenness  of  Wohler's  disappointment  is  more  definitely  ex 
pressed  in  his  letter  to  Liebig  of  January  2,  1831,  in  which  he  wrote: 

...  at  the  moment  I  am  interested  only  in  the  new  Swedish  metal,  vana 
dium,  discovered  by  Sefstrom,  but  really  by  Berzelius.  Ich  war  ein  Esel  not  to 
have  discovered  it  before  in  the  brown  lead  ore  from  Zimapan,  Mexico.  I  was 
engaged  in  analyzing  it  and  had  already  found  in  it  something  new  when,  in 
consequence  of  hydrogen  fluoride  vapor,  I  became  ill  for  several  months  (24) . 

The  cast  iron  in  which  Sefstrom  discovered  vanadium  had  been 
prepared  from  ore  from  the  mine  at  Taberg,  Sm&land.  When  Daniel 
Tilas  described  this  hill  in  1760,  he  stated  that  iron  had  been  smelted 
there  since  1610  and  that  the  supply  of  it  was  still  almost  inexhaustible 
(74).  C.  Beijell  analyzed  this  ore  in  1760  and  found  that  it  contained 
from  21  to  31.5  per  cent  of  iron,  that  it  was  free  from  sulfur  and  arsenic, 
and  that  good,  serviceable  iron  could  be  prepared  from  it  (75). 


356  DISCOVERY  OF  THE  ELEMENTS 


From  Thomas  Thomson's  "Travels  in  Sweden  During  the  Autumn  of  1812" 

Taberg,  Smaland,  Sweden.    Sefstrom  discovered  vanadium  in  iron  from  the 

Taberg  mine. 


Thomas  Thomson,  in  his  "Travels  through  Sweden  in  the  Autumn  of 
1812,"  quoted  Johann  Friedrich  Hausmann's  description  of  this  great 
hill  of  iron  ore.  "The  ironstone  of  Taberg/'  wrote  Hausmann  in  1811, 
"on  the  southeast  and  east  side,  is  quite  irregular;  partly  from  the  many 
loose  blocks,  and  partly  from  the  way  in  which  it  has  been  blown  up  by 
gunpowder.  It  is  more  valuable  on  account  of  its  tractability  and  the 
absence  of  every  hurtful  ingredient  than  on  account  of  the  great  quantity 
of  iron  which  it  yields.  This  varies  from  21  to  32  per  cent.  In  the  hopes 
of  finding  richer  ore,  a  shaft  was  driven  into  the  mountain;  but  these 
hopes  not  being  realized,  the  labour  was  soon  abandoned.  .  .  .  Taberg, 
which  has  been  wrought  since  the  year  1621,  supplies  all  the  furnaces 
in  the  district,  to  the  number  of  fifteen,  with  ore.  That  it  will  continue 
to  furnish  a  source  of  riches  to  the  latest  posterity  must  be  evident  from 
the  slightest  view  of  its  colossial  [sic]  mass'7  (76). 

Thomson  wrote  in  1813:  "The  uppermost  bed,  which  cannot  be  less 
than  370  feet  thick,  has  been  wrought  as  an  iron  ore  these  250  years. 
The  method  is  simply  to  blast  it  with  gunpowder  and  let  it  fall  to  the 
bottom  of  the  hill,  from  which  it  is  taken  to  iron-furnaces  in  the  neighbour 
hood"  (76). 


NIOBIUM    (  COLUMBIUM  ) ,  TANTALUM,   VANADIUM  357 

For  a  description  of  Sefstrom's  method  of  isolating  vanadium,  it  is 
necessary  to  quote  again  from  the  correspondence  of  Berzelius,  this 
time  from  a  letter  to  Dulong.  On  January  7,  1831,  he  wrote: 

I  must  tell  you  of  the  discovery  of  a  new  metallic  substance,  of  which  this 
letter  contains  some  preparations.  .  .  .  The  discovery  was  made  by  Mr. 
Sef strom,  director  of  the  School  of  Mines  at  Falun  who,  wishing  to  examine  a 
kind  of  iron  remarkable  for  its  extreme  softness,  found  in  it,  in  extremely  small 
quantity,  a  substance  whose  properties  appear  to  differ  from  those  of  bodies 
hitherto  known,  but  the  quantity  of  which  was  so  infinitely  small  that  too  much 
expense  would  have  been  necessary  in  order  to  extract  enough  of  it  to  permit  of 
closer  examination.  This  iron  was  taken  from  the  Taberg  mine  in  Smaland, 
which  however  contains  only  traces  of  the  new  body,  but  Mr.  Sefstrom,  having 
found  that  the  cast  iron  contained  more  of  it  than  the  wrought  iron,  concluded 
that  the  scoria  formed  during  the  conversion  of  the  cast  iron  to  malleable  iron 
ought  to  contain  larger  quantities  of  it.  This  proved  to  be  true.  Mr.  Sefstrom 
extracted  portions  of  it  which  sufficed  for  studying  it,  and  during  his  Christmas 
vacation  came  to  see  me,  to  finish  with  me  the  study  of  "the  stranger  (nouveau 
debar que)"  (25). 

Sef  Strom's  own  account  of  the  discovery  is  also  of  great  interest: 

It  is  several  years  [said  he],  since  Rinman,  the  manager  of  the  mine,  in  order  to 
discover  easily  whether  an  iron  was  brittle,  gave  a  method  which  depends  on 
the  circumstance  that  such  an  iron,  when  attacked  by  muriatic  [hydrochloric] 
acid,  gives  a  black  powder.  Having  occasionally  treated  in  this  manner  an  iron 
which  was  not  brittle,  and  finally  some  iron  from  Eckersholm,  I  was  greatly 
surprised  to  recognize  in  the  latter  the  reaction  of  a  brittle  iron,  although  the 
iron  from  Taberg  passes  for  the  most  flexible  and  tenacious  that  we  have.  I 
did  not  then  have  the  leisure  to  investigate  the  nature  of  the  black  powder;  but 
in  April,  1830,  I  resumed  my  experiments  to  see  if  it  contained  phosphorus  or 
any  other  substance,  which  was  for  me  not  without  importance. 

I  dissolved  a  considerable  quantity  of  iron  in  muriatic  acid  [Sefstrom  then 
continued]  and  I  noticed  that,  while  it  was  dissolving,  a  few  particles  of  iron, 
mainly  those  which  deposit  the  black  powder,  dissolved  more  rapidly  than  the 
others,  in  such  a  way  that  there  remained  hollow  veins  in  the  midst  of  the 
iron  bar.  Upon  examining  this  black  powder,  I  found  silica,  iron,  alumina,  lime, 
copper,  and,  among  other  things,  uranium.  I  could  not  discover  in  what  con 
dition  this  substance  was,  because  the  small  quantity  of  powder  did  not  exceed 
two  decigrams,  and,  moreover,  more  than  half  of  it  was  silica.  After  several 
experiments  I  saw  that  it  was  not  chromium,  and  the  comparative  tests  that  I 
made  proved  to  me  that  it  certainly  was  not  uranium.  I  had  sought  to  com 
pare  the  highest  degrees  of  oxidation,  but  I  must  remark  that  vanadium  is  found 
partly  in  the  lower  degree  (26) . 

In  one  of  his  letters  Berzelius  mentioned  to  Wohler  an  unfortunate 
accident:  ".  . .  As  Sefstrom  came  home  to  Falun,"  said  he,  "to  take  up  there 


358 


DISCOVERY  OF  THE  ELEMENTS 


the  study  of  the  vanadium  alloy,  a  student  spilled  about  one  lot  (ten 
grams )  of  dissolved  vanadium  oxide  in  such  a  way  that  none  of  it  could  be 
saved.  Now  he  has  nothing  with  which  he  can  work,  and  must  repeat 
the  entire  preparation  process  on  the  slag"  (27). 

In  May,  1830,  a  careful  comparison  of  vanadium  and  uranium  was 
made  in  Berzelius'  laboratory.  It  was  found  that  vanadium  forms  two 
series  of  compounds,  the  vanadic  and  the  vanadous,  but  Berzelius  and 
Sefstrom  did  not  succeed  in  isolating  the  metal. 


Sir  Edward  (T.  E.)  Thorpe,  1845- 
1925.  English  chemist  famous  for  his 
research  on  the  specific  volumes  of 
liquids  in  relation  to  their  chemical  con 
stitution,  and  for  his  work  on  the  oxides 
of  phosphorus  and  the  compounds  of 
vanadium  done  in  collaboration  with 
Sir  Henry  Rosooe.  Author  of  excellent 
textbooks  of  chemistry  and  of  biog 
raphies  and  essays  in  historical  chem 
istry. 


From  1820  to  1845  Sefstrom  edited  Jernkontorets  Annaler  (Annals  of 
the  Iron  Corporation),  and  in  1826  he  was  awarded  the  gold  medal  of 
the  Manufacturing  Association  for  his  services  to  this  journal  (54). 
Among  his  many  contributions  to  it  were  papers  on  the  composition  of 
refinery  slag,  analyses  of  clay  used  in  the  iron  industry,  analysis  of  a 
highly  titanif erous  iron  ore,  improvements  in  the  manufacture  of  Swedish 
iron,  analysis  of  the  mine  water  attFalun,  and  the  history  of  iron  mining 
in  Sweden.  In  a  report  on  one  of  his  foreign  journeys,  written  for 
Jernkontorets  Annaler,  Sefstrom  said:  "...  I  know  of  no  other  process 
which  has  so  many  niceties,  which  is  so  sensitive  to  outside  influences, 
presents  such  a  wealth  of  highly  interesting  phenomena,  and  offers  such 
an  extensive  field  for  pleasant  research  as  the  preparation  of  bar  iron 
in  the  hearth.  Medicine,  in  which  I  was  engaged  for  several  years,  is 
also  a  great  field  for  investigation;  but  I  have  had  just  as  many  interesting 
conversations  with  thoughtful  smiths  ...  as  I  ever  had  among  my  medical 
acquaintances  .  .  ."  (54,  65). 


NIOBIUM    (  COLUMBIUM  ) ,  TANTALUM,  VANADIUM  359 

Sefstrom  died  at  Stockholm  on  November  30,  1845  at  the  age  of 
fifty-eight  years,  as  the  result  of  a  paralytic  stroke.  The  anonymous 
biography  in  Vetenskapsakaderniens  Handlingar  mentioned  his  large 
stature  and  towering  height,  the  frankness  and  uprightness  of  his  charac- 


-  ti $* > '* ',  ^""-^rv  v^v->£^, 
f, ;,v^;vWV-' >:•?:*  s**r 


Andres  Manuel  del  Rio,  1764-1849.     Spanish-Mexican 
scientist.    For  half  a  century  he  was  professor  of  min 
eralogy  at  the  School  of  Mines  of  Mexico. 

ter,  and  his  tireless  perseverance,  and  added  that  he  gave  to  Swedish  min 
ing  "a  new  direction,  namely  the  scientific,  and  thus  lighted  in  Sweden  a 
new  miners'  lamp,  which  will  never  be  extinguished"  (66). 

After  N.  G.  Sefstrom  had  discovered  vanadium  in  a  soft  cast  iron  from 
Eckersholm,  Sweden,  no  mineral  containing  it  as  an  essential  constituent 
was  known  until  Wohler  analyzed  the  specimen  of  'Thrown  lead  from 
Zimapdn"  which  del  Rio  had  sent  to  Europe  by  Baron  Alexander  von 
Humboldt  (73).  Wohler's  researches  (45)  proved  that  he  had  been 


360 


DISCOVERY  OF  THE  ELEMENTS 


correct  in  believing  that  the  ore  del  Rio  had  analyzed  in  1801  really  con 
tained  vanadium  instead  of  chromium  (26).  This  mineral  is  now  known 
as  vanadinite,  PbCl2-3Pb3(VO4)2. 

The  final  step  in  the  discovery  of  vanadium  was  accomplished  by  the 
English  chemist,  Sir  Henry  Enfield  Roscoe,  who  was  born  in  London  on 
January  7,  1833.  When  he  was  nine  years  old  the  family  moved  to 


Sir  Henry  Enfield  Roscoe, 
1833-1915.  Professor  of 
Chemistry  at  the  Univer 
sity  of  Manchester.  Col 
laborator  with  Bunsen  in 
researches  in  photochem 
istry.  Author  of  excel 
lent  textbooks  and  trea 
tises  on  pure  and  applied 
chemistry. 


From     Thorjjefs     "The     Right 

Honourable  Sir  Henry  Enfield 

Roscoe" 


Liverpool.  One  of  his  first  schoolmasters  reported  that  "Roscoe  is  a  nice 
boy,  but  he  looks  about  him  too  much,  and  does  not  know  his  irregular 
verbs"  (36).  His  mother,  who  evidently  did  not  object  seriously  to 
this  habit  of  "looking  about,"  encouraged  him  to  make  chemical  experi 
ments  at  home  and  allowed  him  to  transform  one  of  the  rooms  into  a 
laboratory. 

At  the  age  of  fifteen  years  the  boy  entered  University  College, 
London,  where  he  studied  under  Thomas  Graham  and  Alexander  Wil 
liam  Williamson.  After  graduating  in  1853  with  honors  in  chemistry, 
he  went  to  Heidelberg  to  study  quantitative  analysis  in  the  old  monastery 
that  had  been  transformed  into  a  laboratory  for  Robert  Bunsen.  After 
passing  his  doctor's  examination  summa  cum  laude,  he  collaborated  with 
Bunsen  in  the  famous  researches  on  the  chemical  action  of  light.  During 
their  long  friendship  Roscoe  received  from  the  great  German  master  one 


NIOBIUM    (  COLUMBIUM  ) ,  TANTALUM,   VANADIUM  361 


hundred  twenty-six  letters,  which  he   carefully  preserved   and  finally 
presented  in  bound  form  to  the  Bunsen-Gesellschaft  (38). 

When  only  twenty-four  years  old,  Roscoe  succeeded  Edward  Frank- 
land  as  professor  of  chemistry  at  the  University  of  Manchester.  In  the 
winter  of  1862,  when  thousands  of  employees  in  the  cotton  mills  of 
Lancashire  were  thrown  out  of  work  because  of  the  Civil  War  in  America, 
Roscoe,  in  an  effort  to  relieve  the  mental  depression  of  the  unemployed, 
instituted  a  series  of  popular  "Science  Lectures  for  the  People."  Roscoe, 
John  Tyndall,  Thomas  Huxley,  and  other  noted  scientists  addressed  large 
and  appreciative  audiences  each  week  for  eleven  consecutive  winters,  and 
the  printed  lectures  were  afterward  sold  for  a  penny  all  over  the  world 


Carl  Friedrich  Rammelsberg,  1813-1899. 

German  chemist,  mineralogist,  and  crys- 
tallographer  who  demonstrated  the  iso 
morphism  of  sulfur  and  selenium  crystals 
obtained  from  carbon  disulfide  solutions 
of  these  elements,  and  showed  that  the 
vanadates  are  isomorphous  with  the  phos 
phates.  He  also  determined  the  crystal 
forms  of  many  organic  compounds,  and 
wrote  textbooks  on  crystallography,  met 
allurgy,  and  mineralogical  and  analytical 
chemistry. 


(39).  In  his  teaching  Roscoe  emphasized  the  need  of  liberal  culture  as 
a  basis  for  technical  training  (28). 

In  about  1865  he  found  that  some  of  the  copper  veins  of  the  Lower 
Keuper  Sandstone  of  the  Trias  in  Cheshire  contained  vanadium  (37) 
and  that  one  of  the  lime  precipitates  from  this  ore  contained  about  two 
per  cent  of  it.  It  was  from  this  unpromising  material  that  Roscoe  and 
Sir  Edward  Thorpe  laboriously  prepared  the  pure  vanadium  compounds 
needed  for  a  thorough  study  of  the  element. 

When  Roscoe  investigated  them  he  found  that  vanadium  is  a  tri-  and 
pentavalent  element  of  the  phosphorus  group.  He  also  discovered  that 
what  Berzelius  had  taken  for  the  metal  was  really  the  mononitride,  VN, 
and  that  most  of  the  vanadium  compounds  studied  by  the  Swedish  chem 
ists  had  contained  oxygen. 


362  DISCOVERY  OF  THE  ELEMENTS 

On  August  26,  1867,  Roscoe  wrote  to  Thorpe  saying, 

...  I  want  you  very  much  to  stay  with  me  till  April  to  settle  the  vana 
dium  and  light  matters  and  help  me  in  London  with  my  lectures.  ...  I' 
have  at  last  found  out  about  vanadium.  The  acid  is  V2O5  like  P2O5.  The 
chloride  VOC13  like  POC13  and  the  solid  chlorides  VOC12,  VOC1,  etc.  This 
explains  the  isomorphism  of  the  vanadate  of  lead  and  the  corresponding  phos 
phate  and  lots  of  other  points.  It  becomes  very  interesting  now  .  .  .  (40). 

On  September  12  of  the  same  year  Roscoe  wrote  again  to  his  assistant: 

Please  ask  Joseph  [Heywood]  to  send  me  per  book-post  Pogg.  Ann.,  vol. 
98,  in  which  volume  is  Rammelsberg's  paper  on  the  isomorphism  of  vanadates 
and  phosphates.  There  is  no  doubt  in  my  mind  that  vanadic  acid  is  V2O5,  and 
it  will  be  exceedingly  interesting  to  work  out  the  vanadates,  which  must  all  be 
explained  as  phosphates.  The  ordinary  white  NH3  salt  is  NH4VO3  (like 
NaPO3)  and  is  a  metavanadate.  The  bi-vanadates  can  also  be  explained,  but 
all  need  re-preparation  and  analysis.  Did  I  tell  you  that  we  have  now  got  V2O5, 
V204,  V203,  V202  (I  wish  we  had  V  also!),  V2O2C16,  V2O2€14,  V2O2C12, 
or  VOC13,  VOC12,  VOC1?  At  St.  Andrews  I  saw  Professor  Heddle;  he  has  a 
crystal  half  apatite  and  half  vanadinite,  and  he  threw  out  the  suggestion  long 
ago  that  vanadic  acid  is  V2O5  .  .  .  (40). 

Five  days  later  Roscoe  sent  Thorpe  a  detailed  report  of  his  experi 
ments  on  the  oxides  of  vanadium  and  said  in  conclusion,  "The  thing  above 
all  others  necessary  for  us  now  is  to  get  the  metaT  (40). 

Roscoe's  first  paper  on  the  subject  was  the  Bakerian  Lecture  read 
before  the  Royal  Society  on  December  19,  1867.  On  February  14,  1868, 
with  Sir  Edward  Thorpe  as  his  assistant,  he  gave  a  demonstration  lecture 
at  the  Royal  Institution  in  which  he  proved  that  the  lemon-colored  chloride 
to  which  Berzelius  had  assigned  the  formula  VC13  actually  contains 
oxygen.  When  the  audience  saw  him  pass  the  vapor  from  a  few  grams 
of  this  chloride,  together  with  pure  hydrogen  gas,  over  red-hot  carbon, 
and  watched  him  test  the  resulting  gas  for  carbon  dioxide  by  passing  it 
into  clear  baryta  water,  it  was  convinced  that  Berzelius'  formula  must 
be  incorrect.  Roscoe  proved  by  analysis  that  the  lemon-colored  chloride 
is  an  oxychloride  now  known  as  vanadyl  chloride,  VOC13  (12,  29). 

When  he  began  his  researches  on  vanadium,  its  compounds  were 
listed  at  £35  per  ounce,  and  the  metal  itself  was  unknown.  After  all 
attempts  at  direct  reduction  of  the  oxides  had  failed,  Roscoe  attempted 
to  reduce  vanadium  dichloride,  VC12,  with  hydrogen.  Rigorous  exclusion 
of  oxygen  and  moisture  was  necessary,  and,  since  vanadium  metal  reacts 
violently  with  glass  and  porcelain,  the  chloride  was  placed  in  platinum 
boats  inside  a  porcelain  tube.  The  tube  itself  could  not  be  made  of 
platinum  because  of  the  porosity  of  that  metal  at  red  heat. 


NIOBIUM  (COLUMBIUM),  TANTALUM,  VANADIUM        363 

When  he  heated  the  tube,  hydrochloric  acid  gas  came  off  in  "torrents," 
and  continued  to  be  evolved  in  decreasing  quantity  for  from  forty  to  eighty 
hours.  When  it  finally  ceased  to  come  off,  the  tube  was  cooled  and  the 
boat  was  found  to  contain  "a  light  whitish  grey-colored  powder,  perfectly 
free  from  chlorine."  When  Roscoe  examined  this  powder  under  the 
microscope,  he  found  that  it  reflected  light  powerfully  and  that  it  consisted 
of  "a  brilliant  shining  crystalline  metallic  mass  possessing  a  bright 
silver-white  lustre."  Roscoe's  paper  announcing  the  isolation  of  metallic 
vanadium  was  read  before  the  Royal  Society  on  June  16,  1869  (33). 

While  studying  at  Heidelberg,  Sir  Edward  Thorpe  read  in  a  French 
periodical  on  popular  science  that  the  Copley  Medal  had  been  awarded 
to  Sir  Henry  E.  Roscoe.  His  letter  of  congratulation  brought  title  follow 
ing  reply: 

In  the  first  place  let  me  thank  you  for  your  letter  and  congratulations  upon 
the  great  French  discovery!  Many  of  these  Parisian  wonders  have  after  all 
turned  out  myths— and  this  last  is,  I  believe,  no  exception— the  expression 
"Medaille  de  Copley"  is,  so  far  as  I  am  aware,  the  French  (and  bad  French, 
too!)  for  the  "Bakerian  Lecture."  I  am,  however,  none  the  less  obliged  to  you 
for  your  good  wishes  on  this  occasion,  and  for  all  the  valuable  help  which  in 
many  ways  you  gave  me  (41 ) . 

Roscoe's  textbooks  of  chemistry  were  unusually  successful,  passed 
through  edition  after  edition,  and  were  translated  into  Russian,  Italian, 
Hungarian,  Polish,  Swedish,  modern  Greek,  Japanese,  Urdu,  Icelandic, 
Bengali,  Turkish,  Malayalam,  and  Tamil.  His  autobiography  (42)  was 
written  with  great  charm,  and  the  "Treatise  on  Chemistry"  by  Roscoe  and 
Schorlemmer  is  familiar  to  all  chemists. 

Sir  Henry's  last  years  were  spent  on  his  beautiful  estate  at  Woodcote 
in  southern  England.  Here  Lady  Roscoe  took  endless  pleasure  in  the 
cultivation  of  flowers  and  flowering  shrubs  and  in  entertaining  her  hus 
band's  distinguished  guests.  "My  father,"  said  Miss  Roscoe,  "delighted 
to  bring  foreigners,  and  the  more  heterogeneous  they  were  the  more  he 
was  pleased.  I  remember  one  luncheon  party  of  late  years,  consisting  of 
a  Chinaman,  a  Japanese,  a  Czech,  a  German,  and  our  three  selves,  and 
the  Occidentals  were  much  the  quietest  of  the  party"  (43). 

After  enjoying  a  serene  old  age,  Sir  Henry  E.  Roscoe  died  suddenly 
on  December  18,  1915,  during  an  attack  of  angina  pectoris. 

In  1927  J.  W.  Marden  and  M.  N.  Rich  of  the  research  staff  of  the 
Westinghouse  Lamp  Company  obtained  metallic  vanadium  99.9  per  cent 
pure  by  heating  a  mixture  of  vanadic  oxide,  metallic  calcium,  and  calcium 
chloride  in  an  electric  furnace  for  an  hour  at  a  temperature  of  about 
1400°  Fahrenheit.  When  the  resulting  mass  was  cooled  and  stirred  into 
cold  water,  beads  of  pure  metallic  vanadium  separated  out  (35). 


364  DISCOVERY  OF  THE  ELEMENTS 

The  alloy  ferrovanadium  is  used  extensively  in  the  steel  industry. 
The  presence  of  small  amounts  of  vanadium  profoundly  alters  the  prop 
erties  of  steel,  greatly  increasing  its  toughness,  elasticity,  and  tensile 
strength.  Thus  the  metal  that  Sefstrom  and  Berzelius  named  for  the 
ancient  Swedish  goddess  of  beauty  has  come  to  play  an  important 
utilitarian  role  in  the  construction  of  locomotive  frames,  driving  axles, 
and  large  shaftings  for  electrical  machinery. 

Patronite.  An  important  commercial  deposit  of  vanadium  is  the 
patronite  of  Peru,  an  impure  sulfide  containing  free  sulfur.  This  ore  was 
first  found  in  1905  at  Minasragra  near  Cerro  de  Pasco,  Peru,  16,000  feet 
above  sea  level,  and  was  named  for  its  discoverer,  Senor  Antenor  Rizo- 
Patron  (77,  78).  Vanadium  is  also  obtained  as  a  by-product  from  the 
exploitation  of  Colorado  carnotite  for  radium  and  uranium  (77). 

Vanadium  in  Plants  and  Animals.  In  1899  Charles  Baskerville 
detected  vanadium  in  the  ashes  of  certain  peats  (77,  79).  M.  Henze 
discovered  in  1911  that  the  blood  of  certain  tunicates  contains  an  organic 
compound  of  vanadium  (77,  80).  He  noticed  that  the  blood  corpuscles 
of  the  ascidian  Phallusia  mamillata  contain  a  chromogen  which  becomes 
yellow-green  to  blue  on  standing.  After  separating  the  corpuscles  with 
a  centrifuge,  he  dissolved  this  chromogen  in  distilled  water.  By  adding 
acetone  to  the  resulting  brown  solution,  he  precipitated  the  chromogen 
and  afterward  separated  it  with  a  centrifuge.  On  burning  it,  and  fuming 
the  ash  with  nitric  acid,  he  obtained  an  orange-red  residue  of  vanadic 
acid  anhydride.  In  a  quantitative  analysis  made  on  a  very  small  portion 
of  the  chromogen,  Henze  found  that  it  contained  more  than  15  per  cent 
of  vanadium  pentoxide  ,(80).  The  vanadium  was  later  found  to  be 
localized  in  specialized  green  cells,  the  vanadocytes.  As  a  result  of 
researches  at  the  Zoological  Station  in  Naples,  Professor  D.  A.  Webb  of 
Cambridge  University  concluded  that  the  vanadium  chromogen  is  not 
a  respiratory  pigment  (81). 

LITERATURE  CITED 

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house  at  Mexico,"  Annals  of  Phil,  [2],  10,  256  (Oct.,  1825). 

(2)  POGGENDORFF,   J.    C.,    "Biographisch-Literarisches    Handworterbuch    zur   Ge- 

schichte  der  exakten  Wissenschaften,"  6  vols.,  Verlag  Chemie,  Leipzig  and 
Berlin,  1863-1937.  Articles  on  Hatchett,  del  Rio,  and  Sefstrom. 

(3)  HATCHETT,  C.,  "Outline  of  the  properties  and  habitudes  of  the  metallic  sub 

stance  lately  discovered  by  Charles  Hatchett,  Esq.,  and  by  him  denominated 
columbium."  Nicholsons  /.,  [2],  1,  32-4  (Jan.,  1802);  Crell's  Ann.,  37,  197- 
201,  257-70,  352-64  (1802). 

(4)  "New  metal  columbium,"  Nicholsons  /.,  14,  181  (June,  1806). 

(5)  THOMSON,  THOMAS,  "History  of  Chemistry,"  Vol.   2,   Colburn  and  Bentley, 

London,  1831,  p.  231. 

(6)  WALLACH,  O.,  "Briefwechsel  zwischen  J.  Berzelius  und  F.  Wohler,"  Vol.  2, 

Verlag  von  Wilhelm  Engelmann,  Leipzig,  1901,  p.  544. 


NIOBIUM  (COLUMBIUM),  TANTALUM,  VANADIUM        365 

(7)  BALKE,  C.  W.,  "Metals  of  the  tungsten  and  tantalum  groups,"  Ind.  Eng.  Chem., 

21,  1002-7  (Nov.,  1929);  C.  W.  BALKE  and  EDGAR  F.  SMITH,  "Observations 
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J.,  25,  23-8  (Jan.,  1810). 

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pp.  341-5. 

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Upsala,  1912-1914,  pp.  18-20. 

(14)  Ibid.,  Vol.  3,  part  6,  p.  25. 

(15)  Ibid.,  Vol.  1,  part  3,  p.  123. 

(16)  Ibid.,  Vol.  1,  part  3,  p.  40. 

(17)  GILES,  "Observations  on  niobium,  tantalum,  and  titanium,"  Chem.  News,  95, 

1-3,  37-9  (Jan.  4  and  Jan.  25,  1907);  W.  VON  BOLTON,  "Das  Niob,  seine 
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(18)  "Rare  Metals,"  Fansteel  Products  Co.,  N.  Chicago,  1929,  pp.  7-22. 

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Eng.,  27,  1271-3  (Dec.  27,  1922). 

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chim.  phys.,  [4],  8,  5—75  (May,  1866);  "Recherches  sur  les  combinaisons 
du  tantale,"  ibid.,  [4],  9,  249-76  (Nov.,  1866). 

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Ann.,  71,  7. 

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(23)  WALLACH,  O.,  "Briefwechsel  zwischen  J.  Berzelius  und  F.  Wohler,"  ref.  (6), 

Vol.  1,  p.  336. 

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(27)  WALLACH,  O.,  "Briefwechsel  zwischen  J.  Berzelius  und  F.  Wohler,"  ref.  (6), 

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(28)  SCHUSTER  and  SHIPLEY,  "Britain's  Heritage  of  Science,"  Constable  and  Co., 

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1925). 


366  DISCOVERY  OF  THE  ELEMENTS 

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(37)  Ibid.,  p.  123. 

(38)  Ibid.,  p.  26. 

(39)  Ibid.,  pp.  38-9. 

(40)  Ibid.,  pp.  125-30. 

(41)  Ibid.,  p.  129. 

(42)  ROSCOE,  H.  E.,  "The  Life  and  Experiences  of  Sir  Henry  Enfield  Roscoe,"  Mac- 

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(44)  VON  HUMBOLDT,  A.,  Gilb.  Ann.,  18,  118  (1804). 

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(72)  DEL  Rio,  A.  M.,  "Elementos  de  orictognosia  .    .    .,"  2nd  ed.,  Juan  F.  Hurtel, 

Philadelphia,  1832,  pp.   483-5. 

(73)  WITTICH,  E.,  "El  descubrimiento  del  vanadio,"  Boletin  Minero,  13,  4-15  (Jan., 

1922);  POGGENDORFF,  Fogg.  Ann.,  21,  49  (1830). 

(74)  TELAS  DANIEL,  "Das  Eisenbergwerk  Taberg  in  Smaland,"  Crell's  Neues  chem. 

Archw,  8,  280-1  (1791);  K.  Vet.  Acad.  Handl,  22,  15  (1760). 

(75^1     BEITELL   C.,  "Proben  vom  Gehalte  des  Eisenerzes  am  Taberge,"  Cretts  Neues 
chem.  Archiv,  8,  281-2  ( 1791 ) ;  K.  Vet.  Acad.  Handl,  22,  28  ( 1760 ). 

(76)  THOMSON,  THOMAS,  "Travels  through  Sweden  in  the  autumn  of  1812,"  Robert 

Baldwin,  London,  1813,  pp.  286-95. 

(77)  FRIEND,  J.  N.,  "A  textbook  of  inorganic  chemistry,"  Vol.  6,  part  3,  Charles 

Griffin  and  Co.,  London,  1929,  pp.  9-13. 

(78)  HILLEBRAND,  W.  F.,  "The  vanadium  sulphide,  patronite,  and  its  mineral  as 

sociates  from  Minasragra,  Peru,"  Am.  J.  Sci.,  (4),  24,  141-51  (1907). 

(79)  BASKERVTLLE  CHARLES,  "The  occurrence  of  vanadium,  chromium,  and  titanium 

in  peats,"  J.  Am.  Chem.  Soc.,  21,  706-7  ( 1899). 

(80)  HENZE,  M.,  "Untersuchungen  iiber  das  Blut  der  Ascidien,"  Z.  physiol  Chem., 

72,494-501  (1911). 

(81)  WEBB,  D.  A.,  "Observations  on  the  blood  of  certain  ascidians,  with  special 

reference  to  the  biochemistry  of  vanadium,"  J.  Exptl  Biol,  16,  499-523 
(1939). 


Charles  Hatchett.  This  portrait  was  lithographed 
by  Day  and  Haghe  from  the  painting  by  Thomas 
Phillips,  and  published  in  1836  by  Thomas  Me 

Lean. 


14 


Contributions  of  Charles  Hatchett 


£7. 


nlike  most  chemists  Charles  Hatchett  spent  all  his  life  in 
luxurious  surroundings.  He  was  born  on  January  2,  1765,*  the  son  of  a 
famous  coach  builder  of  Long  Acre,  London,  who  in  1771  built  at  Chelsea 
a  mansion  called  "Belle  Vue  House"  (I,  2,  3). 

Most  of  his  scientific  research  was  done  during  the  decade  1796  to 
1806.  His  first  paper  in  the  Philosophical  Transactions  described  his 
analysis  of  the  Carinthian  lead  molybdate  (4).  "The  celebrated  Scheele," 
said  he?  "in  1778  read  before  the  Academy  of  Sciences  at  Stockholm  an 
essay  in  which  he  proved  .  .  .  that  the  mineral  called  Molybdaena  was 
composed  of  sulfur  and  a  peculiar  metallic  substance,  which,  like  arsenic 
and  tungsten,  was  liable  by  super-oxygenation  to  be  converted  into  a 
metallic  acid  which  in  its  properties  differed  from  any  other  that  had  been 
previously  discovered."  Hatchett  mentioned  the  confirmatory  researches 
of  B.  Pelletier,  P.  J.  Hjelm,  and  "Mr.  Islmann"  [J.  C.  Ilsemann],  and  added: 
"But  the  existence  of  this  substance  was  known  to  be  only  in  that  mineral 
which  Scheele  had  examined."  This  lead  mineral  from  Carinthia  had 
been  described  by  the  Abbe  F,  X.  Wulfen  and  by  N.  J.  Jacquin.  For 
several  years  it  was  believed  to  be  lead  tungstate,  but  Klaproth  proved 
it  to  be  lead  molybdate.  Since  Klaproth  had  had  an  insufficient  amount 
of  the  mineral,  Hatchett  made  a  complete  analysis  of  it  and  investigated 
the  properties  of  molybdic  acid. 

In  the  following  year  Hatchett  was  made  a  Fellow  of  the  Royal 
Society.  In  1798  he  analyzed  "an  earthy  substance,"  sydneia,  which 
Josiah  Wedgwood  had  found  in  New  South  Wales  and  another  specimen 
of  it  provided  by  Sir  Joseph  Banks  (5).  This,  according  to  Wedgwood, 
was  composed  of  "a  fine  white  sand,  a  soft  white  earth,  some  colourless 
micaceous  particles,  and  some  which  were  black."  Hatchett  found  it 
to  consist  "of  siliceous  earth,  alumine,  oxide  of  iron,  and  black  lead  or 
graphite"  and  concluded  "that  the  Sydneian  genus,  in  future,  must  be 
omitted  in  the  mineral  system." 

*  Most  authors  state  that  Hatchett  was  born  "in  about  1765."  The  1935  "Annuaire" 
of  the  Academic  des  Sciences,  however,  in  its  list  of  members  and  correspondents, 
gives  the  definite  date,  January  2,  1765.  This  annual  gives  the  date  of  his  death  as 
March  10,  1847,  instead  of  February  10. 

369 


370  DISCOVERY  OF  THE  ELEMENTS 

In  the  same  year,  he  analyzed  the  water  of  the  Mere  of  Diss  (6). 
Benjamin  Wiseman  of  Diss,  Norfolk,  had  noticed  that  flint  stones, 
calcareous  spar,  slate,  and  pottery  left  in  this  water  from  the  summer 
of  1792  to  August,  1795,  acquired  a  metallic  stain.  He  sent  some  of  the 
water  and  some  of  the  coated  objects  to  the  President  and  Council  of 
the  Royal  Society,  who  forwarded  them  to  Charles  Hatchett  for  analysis. 
Although  the  deposit  contained  pyrite,  the  water,  according  to  Hatchett, 
did  not  hold  in  solution  any  sulphur  and  scarcely  any  iron;  it  has  not 
therefore  been  concerned  in  forming  the  pyrites,  but  it  appears  to  me 
that  the  pyritical  matter  is  formed  in  the  mud  and  filth  of  the  Mere;  for 
Mr.  Wiseman  says  .  .  .  that  'the  Mere  has  received  the  silt  of  the  streets 
for  ages/  Now  .  .  .  sulphur  is  continually  formed,  or  rather  liberated, 
from  putrefying  animal  and  vegetable  matter,  .  .  .  and  this  most  probably 
has  been  the  case  at  Diss.  .  .  ." 

In  the  following  year  Sir  Everard  Home  interested  Mr.  Hatchett  in 
the  chemical  composition  of  dental  enamel  (7,  8).  Since  the  tooth  of 
the  elephant  is  composed  of  three  different  structures,  Sir  Everard  wished 
to  know  whether  the  materials  themselves  were  different  or  only  differently 
arranged."  Hatchett  showed  that  the  enamel  was  composed  of  calcium 
phosphate.  "The  enamel/'  said  he,  'lias  been  supposed  not  a  phosphate 
but  a  carbonate  of  lime.  This  error  may  have  arisen  from  its  solubility  in 
acetous  acid  or  distilled  vinegar;  but  the  effects  of  the  acetous  acid  are  in 
every  respect  the  same  on  powdered  bone  as  on  the  enamel"  (8). 

Hatchett  then  investigated  the  composition  of  shell  and  bone.  "When 
it  is  applied  to  the  cuttle-bone  of  the  shops  .  .  .  ,"  said  he,  "the  term  bone 
is  here  misapplied  .  .  .  for  this  substance  in  composition  is  exactly  similar 
to  shell,  and  consists  of  various  membranes  hardened  by  carbonate  of 
lime,  without  the  smallest  mixture  of  phosphate"  (8). 

Mr.  Hatchett  observed  that  the  external  skeleton  of  crustaceans  and 
the  egg  shells  of  birds  contain  more  calcium  carbonate  than  calcium 
phosphate  but  that  in  bones  the  phosphate  predominates.  "  It  is  possible/' 
said  he,  "...  that  some  bones  may  be  found  composed  only  of  phosphate 
of  lime:  and  that  thus  shells  containing  only  carbonate  of  lime  and  bones 
containing  only  phosphate  of  lime  will  form  the  two  extremities  in  the 
chain.  .  .  /' 

In  1800  he  published  a  paper  which  won  the  approbation  and 
interest  of  Sir  Humphry  Davy  (9,  10).  "Mr.  Hatchett/'  said  he,  'lias 
noticed  in  his  excellent  paper  on  zoophytes  that  isinglass  is  almost 
wholly  composed  of  gelatine.  I  have  found  that  100  grains  of  good  and 
dry  isinglass  contain  more  than  98  grains  of  matter  soluble  in  water.  .  .  ." 
Dr.  John  Bostock  ( 1774-1846)  also  praised  this  paper.  "The  term  mucus/' 
said  he,  "had  been  generally  employed  in  a  vague  and  unrestricted  sense 
until  Mi1.  Hatchett  .  .  .  attempted  to  assign  to  it  a  more  appropriate  and 


CONTRIBUTIONS  OF  CHARLES  HATCHETT 


371 


definite  meaning.  He  conceives  that  jelly  and  mucus  are  only  modifications 
of  the  same  substance  ...  he  considers  it  to  be  entitled  to  the  appellation 
of  mucus  when  it  is  soluble  in  cold  water  and  cannot  be  brought  to  a 
gelatinous  state  ...  the  ideas  which  I  have  formed  of  the  nature  of  jelly 
and  mucus  .  .  .  differ  materially  from  those  of  Mr.  Hatchett  .  .  .  Mr. 
Hatchett .  . .  speaks  of  the  white  of  the  egg  as  consisting  of  pure  albumen, 
but  I  believe  that  in  this  particular  he  will  be  found  not  perfectly 
accurate.  .  .  ."  Dr.  Bostock  had  found  it  to  contain  also  a  small  amount 
of  a  substance  incapable  of  coagulation  (11). 


William    Thomas    Brande,    1788-1866. 

British  chemist  and  mineralogist.  Suc 
cessor  to  Sir  Humphry  Davy  at  the 
Royal  Institution.  Son-in-law  of  Charles 
Hatchett.  Author  of  Branded  "Manual 
of  Chemistry/*  Lecturer  on  mineralogi- 
cal  chemistry. 


Soon  after  the  turn  of  the  century,  Mr.  Hatchett  became  interested 
in  William  Thomas  Brande,  a  young  apothecaries'  apprentice  who  had 
recently  moved  to  Chiswick.  He  encouraged  the  boy  to  collect  and 
classify  ores  and  rocks,  and  presented  him  with  some  of  his  duplicate 
specimens;  the  boy,  in  turn,  sometimes  assisted  Mr.  Hatchett  in  analyzing 
minerals  (I).  Brande's  first  scientific  paper  was  published  in  Nicholsons 
Journal  when  he  was  only  sixteen  years  old.  When  he  became  Sir 
Humphry  Davy's  successor  at  the  Royal  Institution,  Brande  increased* 
the  mineral  collection  and  used  it  in  his  lectures.  He  later  married 
Charles  Hatchett's  daughter. 

Hatchett's  greatest  achievement  was  probably  his  discovery  of  the 
metal  niobium  (12).  While  he  was  arranging  some  minerals  at  the 
British  Museum,  one  of  them  attracted  his  attention.  From  Sir  Hans 


372  DISCOVERY  OF  THE  ELEMENTS 

Sloane's  catalogue  he  found  that  it  had  been  sent  by  "Mr.  Winthrop  of 
Massachusetts." 

Early  accounts  of  the  discovery  of  columbite  differ  in  several  im 
portant  respects.  While  examining  some  minerals  in  the  British  Museum, 
half  a  century  after  the  death  of  its  founder,  Sir  Hans  Sloane,  Charles 
Hatchett  became  interested  in  a  small,  dark,  heavy  specimen  which 
bore  some  resemblance  to  the  "Siberian  chromate  of  iron"  on  which  he 
was  then  making  some  experiments. 


Dedication        Page        from 
Brande's  "Manual  of  Chem 
istry,"   Third   Edition,    Lon 
don,  1830 


Courtesy  Franklin  Institute 


"Upon  referring  to  Sir  Hans  Sloane's  catalogue,"  said  Hatchett 
before  the  Royal  Society  on  November  26,  1801,  "I  found  that  this 
specimen  was  only  described  as  'a  very  heavy  black  stone,  with  golden 
streaks'  which  proved  to  be  yellow  mica;  and  it  appeared  that  it  had  been 
sent  with  various  specimens  of  iron  ores  to  Sir  Hans  Sloane  by  Mr.  Win 
throp  of  Massachusetts.  The  name  of  the  mine,  or  place  where  it  was 
found,  is  also  noted  in  the  catalogue;  the  writing,  however,  is  scarcely 


CONTRIBUTIONS  OF  CHARLES  HATCHETT 


373 


am 


legible:  it  appears  to  be  an  Indian  name  ( Nautneague ) ;  but  I 
informed  by  several  American  gentlemen  that  many  of  the  Indian  names 
(by  which  certain  small  districts,  hills,  etc.,  were  forty  or  fifty  years  ago 
distinguished )  are  now  totally  forgotten,  and  European  names  have  been 
adopted  in  the  room  of  them.  This  may  have  been  the  case  in  the  present 
instance;  but,  as  the  other  specimens  sent  by  Mr.  Winthrop  were  from 
the  mines  of  Massachusetts,  there  is  every  reason  to  believe  that  the 
mineral  substance  in  question  came  from  one  of  them,  although  it  may  not 
now  be  easy  to  identify  the  particular  mine"  (12). 


Sir  Hans  Sloane,  1660-1753.  British 
physician  and  collector.  Editor  of  the 
Philosophical  Transactions.  President 
of  the  Royal  Society.  The  books,  pic 
tures,  coins,  and  specimens  which  he  be 
queathed  to  the  nation  became  the 
nucleus  of  the  British  Museum.  The 
specimen  of  columbite  in  which  Hat- 
chett  discovered  niobium  was  from  this 
collection. 


Printed  by  C.  Hullmandel 

From  T.  Faulkner's  "Historical  and  topographical 
description  of  Chelsea"  1829 


In  the  following  January,  Nicholsons  Journal  stated  that  "the  mineral 
was  sent  with  some  iron  ores  to  Sir  Hans  Sloane  by  Mr.  Winthrop  of 
Massachusetts  [sic],  and  there  is  therefore  every  reason  to  believe  that 
it  came  from  some  of  the  iron  mines  in  that  province  [sic]"  (12). 

In  the  fall  of  the  same  year,  the  Medical  Repository  made  a  pre 
liminary  announcement  of  Hatchett's  discovery  of  "a  metal  in  an  ore 
lately  brought  from  North-America.  .  .  .  We  have  no  particular  informa 
tion  from  what  spot  or  region  the  mineral  was  procured"  (36). 


374  DISCOVERY  OF  THE  ELEMENTS 


Courtesy  New  Yorfc  Historical  Soci&ty 

Samuel  Latham  Mitchill,  1764-1831.    Professor  of  "chemistry,  natural  his 
tory,  agriculture,  and  the  other  arts  depending  thereon"  at  Columbia  College, 
New  York  City.    Editor  of  the  Medical  Repository,  a  journal  devoted  to  the 
general  progress  of  science.     See  ref,  (50)  and  (54). 


CONTRIBUTIONS  OF  CHARLES  HATCHETT  375 

After  reading  Hatchett's  paper  in  the  Philosophical  Transactions 
Samuel  Latham  Mitchill,  editor,  published  an  abstract  of  it  in 
his  Medical  Repository  (36,  50).  In  commenting  on  the  name  "Naut- 
neague"  he  said,  "From  the  same  place,  it  is  probable,  more  of  the  like 
ore  can  be  obtained.  This  is  particularly  desirable,  as  Mr.  Hatchett  has 
had  so  small  a  piece  to  work  upon,  and  no  other  specimen  but  the  half 
which  he  reserved  for  the  museum  is  known  to  exist.  We  hope  the 
gentlemen  of  Massachusetts,  who  respect  Mr.  Winthrop's  memory  and 
are  acquainted  with  the  scope  and  direction  of  his  researches,  will  find 
out  the  mine  and  procure  more  samples  of  this  singular  mineral.  We 
think  this  matter  would  not  be  unworthy  of  that  excellent  institution  the 
Historical  Society"  (36). 

"No  complete  disoxydation  of  it,"  continued  Mitchill,  'lias  as  yet 
been  effected.  The  pure  metal,  therefore,  has  not  been  seen,  even  by 
Mr.  Hatchett  himself.  And  if  this  discerning  experimenter  had  succeeded 
in  freeing  the  metal  from  its  oxygen,  the  quantity  he  worked  upon  was 
so  very  small  that  it  would  have  been  impossible  to  have  gratified  many 
of  the  curious  by  presents.  At  this  time  it  is  not  known  what  quantity 
may  exist  in  nature,  nor  to  what  economical  uses  it  may  be  applied. 

"While  we  express  our  hopes  that  the  whole  history  of  this  Columbian 
mineral  will  soon  be  made  known,  we  sincerely  deplore  the  afflicting  and 
untimely  death  of  our  friend  and  countryman,  Mr.  Thomas  P.  Smith,  from 
whose  industry,  acuteness,  and  zeal  in  chemical  ( and,  indeed,  almost  the 
whole  circle  of  physical)  researches,  Mr.  Hatchett  informs  the  Royal  So 
ciety  he  had  anticipated  important  aid  in  this  inquiry"  (36). 

In  his  annual  oration  before  the  Chemical  Society  of  Philadelphia  in 
1798,  this  youthful  chemist  voiced  his  conviction  that  "The  only  true 
bases  on  which  the  Independence  of  our  country  can  rest  are  Agriculture 
and  Manufactures.  To  the  promotion  of  these  nothing  tends  in  a 
higher  degree  than  Chemistry.  ...  It  is  to  a  general  diffusion  of 
a  knowledge  of  this  science,  next  to  the  Virtue  of  our  countrymen,  that 
we  are  to  look  for  the  firm  establishment  of  our  Independence"  (47). 
In  the  return  journey  from  England,  Thomas  P.  Smith  died  "in  conse 
quence  of  the  bursting  of  a  gun"  at  the  age  of  only  twenty-five  years 
(36).  Mrs.  Gertrude  D.  Hess,  assistant  librarian,  kindly  searched  the 
manuscripts  of  the  American  Philosophical  Society  by  and  pertaining  to 
Thomas  P.  Smith,  but  was  unable  to  find  there  any  mention  of  columbite. 

In  the  spring  of  1805  the  Medical  Repository  published  an  article 
entitled  "Place  where  the  ore  of  columbium  was  found"  (37).  "It  has 
been  ascertained,"  the  article  stated,  "that  the  specimen  of  this  metal  [sic] 
upon  which  the  experiments  were  made,  as  mentioned  in  Our  Med.  Rep. 
Hex.  i,  vol.  vi.,  p.  322,  was  taken  from  a  spring  of  water  in  the  town  of 
New  London,  in  the  State  of  Connecticut.  The  fountain  is  near  the 


376  DISCOVERY  OF  THE  ELEMENTS 

house  in  which  Governor  Winthrop  used  to  live,  and  is  about  three  miles 
distant  from  the  margin  of  salt  water,  at  the  head  of  the  harbour.  This 
is  the  spot  heretofore  called  Nautneague;  which  is  in  Connecticut  and 
not  in  Massachusetts.  By  the  politeness  of  Francis  B.  Winthrop,  Esq., 
of  New  York,  the  manuscript  papers  of  his  ancestor,  relative  to  this  place 
and  to  the  minerals  he  carried  to  Hans  Sloane,  have  been  sent  to  the 
Historical  Society  of  Massachusetts.  By  their  care,  we  hope,  every 
interesting  particular  concerning  this  substance  and  the  place  where  it 
was  originally  found  will  be  made  known  to  the  public.  It  will  then  be 
easy  for  gentlemen  to  visit  the  spot  and  to  collect  other  specimens  of 
this  singular  ore"  (37). 

In  the  same  year  A.-L.  Millin  published  in  his  Magasin  Encyclope- 
dique  what  seems  to  be  a  rather  inaccurate  French  translation  of  the 
preceding  article.  He  said  he  had  obtained  the  information  from  M. 
Valentin,  a  physician  and  skilful  physicist  and  naturalist  of  Marseilles 
(SS). 

The  "Mr.  Winthrop  of  Massachusetts"  referred  to  by  Charles 
Hatchett  was  John  Winthrop  (1681-1747),  grandson  of  the  first  governor 
of  Connecticut  and  great  grandson  of  the  first  governor  of  Massachusetts. 
He  was  a  Fellow  and  very  active  member  of  the  Royal  Society.  Like  his 
paternal  grandfather,  who  had  been  one  of  the  original  Fellows  of  this 
Society,  he  liked  to  collect  natural  objects.  The  Journal  Book  of  the 
Royal  Society  for  June  27,  1734,  stated  that  "Mr.  Winthrop  presented 
several  curiosities  from  New  England,  as  contained  in  the  following 
list.  .  .  .  These  curiosities  are  a  part  of  a  large  collection  shewn  at 
several  meetings  during  the  subsequent  winter,  and  the  whole  cata 
logue  to  which  these  numbers  refer  is  entered  after  the  minutes  of 
the  day"  (39).  Sir  Hans  Sloane  was  then  President  of  the  Royal  Society 
(40). 

In  1844  Benjamin  Silliman  and  Benjamin  Silliman,  Jr.,  published  this 
historic  list  in  their  American  Journal  of  Science  and  remarked  in  a  foot 
note  "it  has  been  supposed  that  the  original  specimen  on  which  Mr.  Hatch 
ett  made  the  discovery  of  columbic  acid  was  sent  in  this  invoice,  and  that 
some  hint  as  to  the  locality  from  whence  it  came  might  be  had"  (39). 
The  only  entry  the  Sillimans  could  find  in  this  list,  however,  that  corre 
sponded  at  all  with  Hatchett's  description  of  columbite  was  "No.  348. 
A  black  mineral,  very  heavy,  from  the  inland  parts  of  the  country." 
They  concluded  that  "we  must  therefore  rest  content  probably  in 
ignorance  of  the  exact  locality  of  that  interesting  specimen,  although 
mineralogists  have,  on  what  evidence  does  not  appear,  considered  New 
London  as  the  locality"  (39). 

Berzelius  even  doubted  the  American  origin  of  columbite.  In  a 
letter  to  Thomas  Thomson  in  the  autumn  of  1814  (see  page  349),  he 


CONTRIBUTIONS  OF  CHABLES  HATCHETT  377 

stated  that  "Mr.  Hatchett  gave  this  name  after  the  place  where  it  was 
thought  the  fossil  had  been  found;  now  it  is  not  good  practice  to  name  ele 
mentary  substances  in  chemistry  after  the  places  where  they  have  first 
been  found;  not  to  mention  the  fact  that  the  place  where  columbite  was 
found  is  still  doubtful,  in  the  same  degree  as  it  is  not  certain  that  it 
comes  from  America." 

In  his  "Report  on  the  Geological  Survey  of  the  State  of  Connecticut/' 
Dr.  Charles  Upham  Shepard  said  of  columbite:  "The  State  of  Connecticut 
furnished  the  first  sample  of  this  ore  to  science.  .  .  .  The  chinastone 
quarry  at  Middletown  has  furnished  the  most  extraordinary  specimens  of 
columbite  yet  described  in  the  world.  A  single  group  of  crystals  obtained 
at  this  place  weighed  fourteen  pounds.  ...  It  is  also  found  in  smaU 
quantity  at  Haddam. . .  .  The  first  sample  was  sent  by  Governor  Winthrop 
to  Sir  Hans  Sloane,  and  was  deposited  with  the  collection  of  the  gentle 
man  in  the  British  Museum,  where  it  was  examined  by  Mr.  Hatchett,  and 
afterwards  by  Dr.  Wollaston.  The  specimen  was  supposed  to  have  been 
found  near  New  London,  which  was  the  residence  of  Governor  Winthrop; 
but  as  the  ore  has  not  been  rediscovered  in  that  vicinity,  it  is  more 
probable  that  it  was  obtained  from  the  region  of  Middletown"  ( 41 ) . 

Since  Sir  Hans  Sloane  was  only  sixteen  years  old  when  Governor 
Winthrop  died,  Shepard's  statement  that  the  columbite  had  been  sent 
to  Sloane  by  Governor  Winthrop  is  probably  erroneous.  Hatchetfs 
remark  in  1801  that  many  Indian  names  (such  as  Nautneague)  which 
were  used  "forty  or  fifty  years  ago  .  .  .  are  now  totally  forgotten"  implies 
that  he  understood  that  the  original  specimen  of  columbite  must  have 
been  labeled  in  about  the  middle  of  the  eighteenth  century  (12).  He 
referred  to  the  sender,  moreover,  not  as  "Governor"  Winthrop  but  as 
"Mr."  Winthrop. 

In  his  "Chemistry  in  Old  Philadelphia"  Edgar  F.  Smith  stated  that 
"Hatchett  found  ...  a  new  element  in  a  mineral  of  the  Royal  Society 
Collection  which  had  been  sent  in  from  Haddam,  Connecticut,  and  been 
called  there  columbite  by  Governor  Winthrop"  (42). 

In  an  article  on  the  lif e  and  mineral  collection  of  Sir  Hans  Sloane, 
Jessie  M.  Sweet  states  that  "The  only  specimen  which  fortunately  is  still  in 
the  Mineral  Collection  is  the  original  fragment  of  columbite  (B.  M. 
60309 ) ,  of  which  a  brief  account  may  be  given  here.  Sloane  describes 
it  in  the  catalogue  of  'Metalls/  No.  2029,  as:  A  very  heavy  black  stone  with 
golden  streaks  .  .  .  from  Nautneague.  From  Mr.  Winthrop"  (40). 

Miss  Sweet  adds  that  when  John  Winthrop  (1681-1747)  was  elected 
a  Fellow  of  the  Royal  Society  in  1734,  'lie  presented  more  than  six  hundred 
specimens  (mostly  minerals),  together  with  a  manuscript  catalogue  of 
them,  to  the  Society.  .  .  .  Many  of  these  specimens  appear  to  have  been 
incorporated  into  the  Sloane  collection,  as  several  entries  in  the  Winthrop 


378 


DISCOVERY  OF  THE  ELEMENTS 


and  Sloane  manuscript  catalogues  are  identical,  and  the  columbite  prob 
ably  came  from  Winthrop  at  that  time'*  (40). 

Miss  Sweet  also  stated  that  "it  was  surmised  that  TSTautneague'  was 
another  name  for  Naumeaug  (now  New  London,  Connecticut),  and 
the  specimen  was  believed  to  have  been  found  in  a  spring  of  water, 
near  the  house  of  Governor  Winthrop.  .  .  .  The  columbite  is  figured  and 
described  in  James  Sowerby's  "Exotic  Mineralogy/'  1811-1820,  vol.  1,  p.  11 
and  plate  6,  and  compares  favourably  with  Sloane's  description,  but 
now  the  specimen  has  no  longer  any  'golden  streaks' "  (40) . 


John  Winthrop,  1681- 
1747.  The  specimen  of 
columbite  which  Hatchett 
analyzed  had  been  sent  to 
the  Royal  Society  by  this 
John  Winthrop,  a  grandson 
of  John  Winthrop,  first  gov 
ernor  of  Connecticut.  This 
portrait  was  reproduced 
from  a  copy  in  the  collec 
tions  of  the  Massachusetts 
Historical  Society.  Volume 
40  ( 1737-38 )  of  the  Philo 
sophical  Transactions  was 
dedicated  to  him  by  Crom 
well  Mortimer,  Secretary 
of  the  Royal  Society. 


Courtesy  Massachusetts  Historical  Society 


In  1940  Dr.  C.  A.  Browne  wrote  Mr.  Allyn  B.  Forbes  of  the  Massa 
chusetts  Historical  Society  for  information  regarding  the  manuscript 
paper  which  Francis  B.  Winthrop  of  New  York  is  said  to  have  sent  to 
this  Society.  According  to  Nicholson's  Journal  for  1806,  this  manuscript 
referred  to  the  mineral  which  F.  B.  Winthrop's  "ancestor"  had  given  Sir 
Hans  Sloane  and  to  the  place  where  it  was  found  (43),  However,  no 
trace  of  such  a  document  could  be  found.  Francis  B.  Winthrop  (1754- 


CONTRIBUTIONS  OF  CHARLES  HATCHETT  379 

1817)  was  a  grandson  of  John  Winthrop  (1681-1747)   and  great-great- 
grandson  of  the  first  governor  of  Connecticut  (44). 

The  Massachusetts  Historical  Society  has  preserved  a  commonplace 
book  which  originally  belonged  to  John  Winthrop  (1681-1747).  In  it 
there  is  a  letter  which  Francis  B.  Winthrop  wrote  to  his  brother  Thomas 
L.  Winthrop  of  Boston  on  September  10,  1803,  describing  the  spring  at 
New  London  in  connection  with  their  grandfather.  "I  think  you  must 


To  the  Honourable 

JOHN 

Fellow  of  the" ROYAL  SOCIETY. 

s  i  R, 

I  Beg  Leave  to  make  this  Addrefs  to 
you  in  Confi deration  of  thofe  ex-' 
cellent  Virtues  and  rare  Accomplifti- 
mcnts,  with  which  you  are  endowed 
both  as  a  Gentleman  and  a  Scholar, 
Your  great  Knowledge  of  the  true  and 
rnoft  fecret  Branches  of  Philofophy, 
which  has  been  for  many  Generations 
handed  down  in  your  honourable  Fa 
mily  ;  your  profound  Skill  in  all  mi 
neral  Affairs,  particularly  in  Metallurgy, 
which  you  have  likewife  inherited  from 
your  noble  and  truly  learned  Anceftors, 
of  which  you  have  given  ample  Proofs 
by  thofe  curious  Collections  of  American 
Miner ah>  wherewith  you  have  enriched 
the  Mtifeftms  both  of  the  Royal  Soctety, 
of  which  you  are  an  illuftrious  Orna- 
A.  ment 


DEDICATION. 

ment  as  well  as  worthy  Member,  and 
of  their  learned  and  moft  eminent  Pre- 
fident  the  Honourable  Sir  Hans  Sloans 
Baronet  :  Your  perfonal  -Acquaintance 
with  our  ingenious  Latm  Author  Dr. 
Cramer,  who  cannot  but  greatly  ap 
prove  of  my  dedicating  to  you  a  Tranf- 
lation  of  his  excellent  Book  on  the  doci- 
inaftic  Art  ;  thefe,  Sir,  have  been  the 
Motives,  for  which  I  could  not  more 
juftly,  nor  more  judicioufly  £helter  this 
my  new  Performance  under  any  other 
Name,  than  yours. 

However,  Sir,  I  fliall  always  take  it 
as  a  Singular  Favour  done  me,  if  you 
will  be  pleafed  to  accept  this  Tender  of 
my  Refpecl,  as  a  Teftimony  of  the  vaft 
Efteem  and  ftncere  Friendfhip,  where 
with  I  have  the  Honour  to  be, 

SIR, 

Tour  mvft  obcdtcntt 

Aid  tmjl  bumble  Servant, 


London, 
/iyi,  1741. 


Dedication  of  the  English  Translation  of  J.  A.  Cramer's  "Elements  of  the  Art 

of  Assaying  Metals,"  London,  1741.     It  refers  to  John  Winthrop   (1681- 

1747 ) ,  grandson  of  the  first  governor  of  Connecticut. 

remember  this  spring,"  said  he,  "It  is  about  three  miles  from  the  sea,  which 
answers  to  the  distance  in  the  memo  of  articles  presented  to  the  Royal 
Society"  (45). 

In  the  letters  of  Governor  John  Winthrop  the  Younger,  published 
with  the  Winthrop  Papers  of  the  Massachusetts  Historical  Collections, 
there  is  no  mention  of  columbite.  His  interest  in  minerals,  despite  the 
difficulty  of  collecting  them,  is  expressed,  however,  in  a  letter  to  Sir 


380  DISCOVERY  OF  THE  ELEMENTS 

Robert  Moray  on  August  18,  1668.  "I  have  been  very  inquisitive;'  wrote 
the  Governor,  "after  all  sorts  of  minerals,  wcla  this  wildemesse  may 
probably  affoard;  but  indeed  the  constant  warrs,  wch  have  continued 
amongst  the  Indians  since  I  came  last  over,  hath  hindred  all  progresse 
in  searching  out  such  matters.  .  .  .  Those  shewes  of  minerals,  wch  we 
have  fro  the  Indians  doe  only  demonstrate  that  such  are  in  reality  in 
the  country,  but  they  usually  bring  but  small  pieces,  wch  are  found  acci 
dentally  in  their  huntings,  sticking  in  some  rock  or  on  the  surface  of  the 
earth,  on  the  side  of  some  hill,  or  banke  of  a  river  .  .  ."  (46). 

From  the  existing  evidence,  it  seems  impossible  to  prove  conclusively 
whether  columbite  was  discovered  by  John  Winthrop  the  Younger,  first 
governor  of  Connecticut,  and  bequeathed  to  his  grandson,  John  Win 
throp  (1681-1747),  or  whether  it  was  originally  discovered  by  the 
grandson.  It  is  possible,  however,  that  this  question  may  some  day  be 
settled  by  the  finding  of  hitherto  unknown  documents. 

Hatchett  fused  the  ore  with  potassium  carbonate.  When  he  took 
up  the  melt  with  boiling  water,  a  brown  residue  remained.  When  nitric 
acid  was  added  to  the  yellow  filtrate,  a  copious  white  precipitate  was 
thrown  down.  "The  preceding  experiments  shew,"  said  he,  "that  the 
ore  which  has  been  analyzed  consists  of  iron  combined  with  an  unknown 
substance  and  that  the  latter  constitutes  more  than  three  fourths  of  the 
whole.  This  substance  is  proved  to  be  of  a  metallic  nature  by  the 
coloured  precipitates  which  it  forms  with  prussiate  of  potash  and  with 
tincture  of  galls;  by  the  effects  which  zinc  produces  when  immersed  in 
the  acid  solutions;  and  by  the  colour  which  it  communicates  ...  to 
concrete  phosphoric  acid,  when  melted  with  it  ...  ."  He  mentioned 
that  it  retained  oxygen  tenaciously  and  that  the  oxide  was  acidic.  Al 
though  the  specimen  Hatchett  analyzed  was  very  small,  he  hoped  to 
get  more  soon  from  "a  gentleman  now  in  England  ( Mr,  Smith,  Secretary 
to  the  American  Philosophical  Society)."  This  was  evidently  Thomas 
P.  Smith,  who  died  in  1802  (53) . 

Hatchett  named  the  new  metal  columbium  and  stated  that  its  "olive 
green  prussiate  and  the  orange- coloured  gallate  .  .  .  may  probably  be 
employed  with  advantage  as  pigments."  He  also  described  his  un 
successful  attempts  to  reduce  the  oxide  to  the  metal.  From  his  careful 
use  of  Lavoisier's  new  nomenclature,  it  is  evident  that  Hatchett  was  not 
a  phlogistonist. 

In  1798  the  Committee  of  Privy  Council  for  considering  the  state 
of  the  coinage  reported  that  the  gold  coin  was  suffering  considerable 
losses  in  weight,  and  requested  Henry  Cavendish  and  Charles  Hatchett 
to  examine  it  "to  ascertain  whether  this  loss  was  occasioned  by  any 
defect"  (13).  Their  experiments  were  begun  near  the  end  of  1798  and 
completed  in  April,  1801.  At  Cavendish's  request  the  report  was  made 


CONTRIBUTIONS  OF  CHARLES  HATCHETT 


381 


by  Hatchett  alone.  Hatchett  stated,  however,  ".  .  .  At  all  times  I  was 
favoured  with  his  valuable  advice;  and  the  machines  to  produce  friction, 
as  well  as  the  dies  were  entirely  contrived  by  himself.  .  .  " 

Hatchett  studied  the  binary  alloys  of  gold  with  arsenic,  antimony, 
zinc,  cobalt,  nickel,  manganese,  bismuth,  lead,  tin,  iron,  platinum,  copper, 
and  silver,  and  confirmed  the  prevailing  opinion  that  of  these  metals  only 
copper  and  silver  are  suitable  for  alloying  gold  for  coinage.  He  concluded 
"that  gold  made  standard  by  silver  and  copper  is  rather  to  be  preferred 
for  coin  .  .  ."  and  added  that  "there  is  commonly  some  silver  in  the  gold 


(Phil.  Trans.,  1803) 

Apparatus  Designed  by  Henry  Cavendish  and  Used  by 
Charles  Hatchett  for  Determining  the  Comparative  Wear  of 
Gold  When  Alloyed  by  Various  Metals.  Two  frames,  one 
above  the  other,  each  carrying  twenty-eight  coins,  rubbed 
the  upper  coins  backward  and  forward  over  the  ones  below. 
Each  of  the  smaller  concentric  circles  represents  a  coin.  To 
avoid  the  formation  of  furrows,  the  direction  in  which  the 
coins  rubbed  against  each  other  was  made  to  vary  continually. 


which  is  sent  to  the  Mint."  He  also  stated,  not  without  humor,  that  "our 
gold  coin  suffers  but  little  by  friction  against  itself;  and  the  chief  cause 
of  natural  and  fair  wear  probably  arises  from  extraneous  and  gritty 
particles;  .  .  .  the  united  effect  of  every  species  of  friction  to  which  they 
may  be  subjected,  fairly  and  unavoidably,  during  circulation  .  .  .  will 
by  no  means  account  for  the  great  and  rapid  diminution  which  has  been 
observed  in  the  gold  coin  of  this  country.  .  .  ."  He  added  that  the  study 
of  alloys  had  not  kept  pace  with  the  rapid  progress  of  chemistry  and 
that  "Few  additions  have  been  made  to  the  compound  metals  employed 
by  the  ancients." 

In  1804  Hatchett  published  an  analysis  of  a  "triple  sulphuret  of  lead, 


382  DISCOVERY  OF  THE  ELEMENTS 

antimony,  and  copper."  James  Smithson  (1765-1829),  founder  of  the 
Smithsonian  Institution,  disagreed  with  his  conclusions.  "It  is  not 
probable/'  said  he,  "that  the  present  ore  is  a  direct  quadruple  combination 
of  the  three  metals  and  sulphur  and  that  these,  in  their  simple  states, 
are  its  immediate  component  parts;  it  is  much  more  credible  that  it  is 
a  combination  of  the  three  sulphurets  of  these  metals  .  .  ."  (14,  IS). 

At  the  same  time  Hatchett  became  interested  in  lac  (16).  Geoffroy 
the  Younger  and  J.-A.-C.  Chaptal  had  regarded  it  as  a  kind  of  wax,  but 
F.  C.  Cren  and  A.-F.  de  Fourcroy  believed  it  to  be  a  true  resin.  Hatchett 
concluded  "that  although  lac  is  indisputably  the  production  of  insects, 
yet  ...  the  greater  part  of  its  aggregate  properties,  as  well  as  of  its  com 
ponent  ingredients,  are  such  as  more  immediately  appertain  to  vege 
table  bodies.  .  .  " 

In  1804  he  analyzed  a  strongly  magnetic  specimen  of  pyrite  (17)  to 
determine  whether  the  magnetic  polarity  was  inherent  in  the  iron  sulfide 
or  whether  minute  particles  of  "the  ordinary  magnetical  iron  ore"  [mag 
netite]  were  interspersed  in  it.  Although  he  could  find  no  previous  men 
tion  of  magnetic  iron  sulfide,  Hatchett  proved  experimentally  "that  the 
three  inflammable  substances,  carbon,  sulphur,  and  phosphorus .  . .  possess 
the  property  of  enabling  iron  to  retain  the  power  of  magnetism.  .  .  ." 

He  continued  the  study  of  bitumens  which  he  had  begun  in  1798 
and  strengthened  the  evidence  "that  bituminous  substances  are  derived 
from  the  organized  kingdoms  of  nature,  and  especially  from  vegetable 
bodies."  He  analyzed  a  "schistus"  (18)  which  Sir  Joseph  Banks  had  dis 
covered  near  a  geyser  near  Reykum,  Iceland,  and  found  it  to  consist  of 
water,  oily  bitumen,  mixed  gas,  charcoal,  silica,  oxide  of  iron,  and  alumina. 

When  Sir  James  Hall  (1761-1832)  read  of  this  work,  he  recalled  his 
own  experiments  on  "the  effects  of  compression  in  modifying  the  effects 
of  heat/'  and  concluded  that  "the  changes  which,  with  true  scientific 
modesty,  he  [Hatchett]  ascribes  to  an  unknown  cause,  may  have  resulted 
from  various  heats  acting  under  pressure  of  various  force"  (19).  Sir 
James  subjected  the  theories  of  the  geologists  to  the  test  of  chemical 
experiment  and  showed  that  when  limestone  is  heated  under  pressure, 
it  is  not  converted  into  quicklime  but  into  crystalline  marble. 

After  analyzing  some  specimens  from  a  pitch  lake  of  Trinidad, 
Hatchett  concluded  that  "a  considerable  part  of  the  aggregate  mass  at 
Trinidad  was  not  pure  mineral  pitch  or  asphaltum,  but  rather  a  porous 
stone  of  the  argillaceous  genus,  much  impregnated  with  bitumen.  The 
specimens  he  analyzed,  however,  were  not  representative  of  the  lake  as 
a  whole"  (20). 

In  1804  William  Nicholson,  the  editor,  chose  Mr.  Hatchett  and  Ed 
ward  Howard  to  serve  with  him  on  a  committee  to  judge  Richard 
Chenevix's  alloy  of  platinum  and  mercury  which  Chenevix  believed  identi- 


CONTRIBUTIONS  OF  CHARLES  HATCHETT  383 

cal  with  palladium,  the  new  metal  which  had  been  announced  anony 
mously  by  W.  H.  Wollaston.  Hatchett  saw  with  his  own  eyes  some  of  the 
experiments  made  by  the  enthusiastic  but  misguided  Chenevix. 

During  the  years  1805  and  1806  Hatchett  published  three  papers 
on  an  artificial  tanning  agent  (21).  He  mentioned  the  researches  of 
Nicolas  Deyeux  (1745-1837),  Armand  Seguin  (1767-1835),  and  Sir 
Humphry  Davy  on  the  natural  tanning  agents,  and  added  that  R. 
Chenevix  had  "observed  that  a  decoction  of  coffee-berries  did  not  pre 
cipitate  gelatine  unless  they  had  been  previously  roasted;  so  that  tannin 
had  in  this  case  either  been  formed  or  had  been  developed  from  the  other 
vegetable  principles  by  the  effects  of  heat." 

Hatchett  treated  various  kinds  of  wood,  coal,  and  coke  with  nitric 
acid  and  found  that  "a  substance  very  analogous  to  tannin  .  .  .  may  at 
any  time  be  produced  by  exposing  carbonaceous  substances,  whether 
vegetable,  animal,  or  mineral,  to  the  action  of  nitric  acid."  He  also 
"converted  skin  into  leather  by  means  of  materials  which,  to  professional 
men,  must  appear  extraordinary,  such  as  deal  sawdust,  asphaltum,  com 
mon  turpentine,  pit  coal,  wax  candle,  and  a  piece  of  the  same  sort 
of  skin.  .  .  ." 

Dr.  John  Bostock  tried  unsuccessfully  to  use  Hatchetfs  artificial  tan 
as  a  test  for  "jelly"  [gelatine].  Although  it  had  been  stated  "on  the  highest 
authority,  that  of  Mr.  Hatchett  and  Mr.  Davy  .  .  .  that  isinglass  consists 
of  nearly  pure  jelly,"  Dr.  Bostock  found  that  isinglass  from  the  shops 
contained  a  certain  amount  of  insoluble  matter  which  he  believed  to  be 
coagulated  albumen.  Dr.  G.  Melandri  of  Milan  also  investigated  Hatch- 
ett's  tannin. 

M.-E.  Chevreul,  near  the  beginning  of  his  surprisingly  long  career, 
studied  Hatchett's  papers  and  prepared  some  of  the  "tannin."  Hatchett 
had  found  that  pit  coal  which  contained  no  resinous  substance  was 
dissolved  completely  by  nitric  acid  and  converted  into  the  artificial 
tannin,  whereas  any  resinous  matter  remained  undissolved.  When 
Chevreul  treated  pit  coal  with  nitric  acid,  however,  evaporated  the 
solution,  and  poured  it  into  water,  "a  yellow  matter  separated,  which 
was  much  more  abundant  than  "what  remained  in  solution,  and  had  no 
property  that  rendered  it  similar  to  resins  .  .  .  yet  I  do  not  allow  myself," 
said  Chevreul,  "the  least  reflection  on  the  labours  of  that  celebrated 
English  chemist,  as  I  am  too  fully  aware  that  different  modes  of  operat 
ing  and  the  different  varieties  of  the  bodies  examined  .  .  .  may  produce 
a  variation  in  the  results.  .  .  ."  Chevreul  found  that  the  water-soluble 
substance  which  precipitated  gelatine  copiously  was  "a  compound  of 
nitric  acid  and  carbonaceous  matter  „  .  /*  (22).  These  artificial  tannins 
have  since  been  identified  as  picric  acid  and  other  nitro  derivatives  of 
phenols  (23). 


384 


DISCOVERY  OF  THE  ELEMENTS 


Thomas  Thomson  said  in  1810,  "Till  lately  the  analysis  of  vegetable 
substances  was  almost  entirely  overlooked  by  British  chemists;  but  the 
fineness  of  the  field  has  now  begun  to  attract  their  attention.  Experi 
ments  of  great  importance  have  been  published  by  Davy,  Chenevix  &c 
and  above  all  by  Hatchett  .  .  ."  (24). 


Michel-Eugene  Chevreul,  1786-1889.  French  chemist  and  psychologist  who 
made  notable  contributions  to  the  chemistry  of  fats  and  oils,  soap,  candles, 
and  dyes.  He  lived  to  be  almost  one  hundred  and  three  years  old,  sound  and 
active  in  mind  and  body.  When  he  investigated  Hatchett's  artificial  tanning 
agents,  Chevreul  was  only  twenty-four  years  old  (twenty-one  years  younger 
than  Hatchett).  See  refs.  (48,  49,  and  52). 


On  February  21,  1809,  Hatchett  became  a  member  of  the  famous 
Literary  Club  which  had  been  founded  in  1764  by  Dr.  Samuel  Johnson 
and  Sir  Joshua  Reynolds  (51).  As  treasurer  of  the  club,  Hatchett  pre 
pared  a  brief  historical  account  of  it,  which  appears  in  BoswelTs  "Life 
of  Johnson"  (25).  The  club  also  included,  among  others,  Edmund  Burke, 
Oliver  Goldsmith,  David  Garrick,  Edward  Gibbon,  Adam  Smith,  Sir 
Joseph  Banks,  Sir  Charles  Blagden,  Sir  Humphry  Davy,  Dr.  W.  H. 
Wollaston,  Sir  Walter  Scott,  Sir  Thomas  Lawrence,  and  Dr.  Thomas 
Yoimg. 


CONTRIBUTIONS  OF  CHARLES  HATCHETT  385 

Hatchett  also  took  an  active  part  in  the  Animal  Chemistry  Club, 
which  met  alternately  at  his  home  and  that  of  Sir  Everard  Home.  Once 
every  three  months,  Sir  Benjamin  Brodie,  Sir  Humphry  Davy,  W.  T. 
Brande,  Mr.  John  George  Children,  and  a  few  others  dined  with  the 
two  hosts  and  discussed  their  researches  in  physiological  chemistry 
(26,  27,  28}.  According  to  Sir  Benjamin  Brodie,  "they  were  very  rational 
meetings,  in  which  a  good  deal  of  scientific  discussion  was  mixed  up  with 
lively  and  agreeable  conversation.  The  society  continued  to  exist  for 
ten  or  eleven  years,  but  during  the  latter  part  of  the  time,  some  other 
members  were  added  to  it,  and  it  degenerated  into  a  mere  dinner  club. 
Hatchett,  who  had  now  inherited  a  considerable  fortune  on  the  death  of 
his  father,  had  ceased  to  work  in  chemistry  (in  spite  of  the  remonstrance 
of  Sir  Joseph  Banks,  who  used  to  say  to  him  in  his  rough  way  that  'he 
would  find  being  a  gentleman  of  fortune  was  a  confounded  bad  trade'), 
but  he  had  previously  laid  up  a  large  store  of  knowledge,  abounded  in 
the  materials  of  conversation,  and  was  a  delightful  companion  ..."  (28). 

Hatchett  was  one  of  the  "educated  men,  with  the  sagacity  for  which 
this  nation  is  famous"  who  helped  to  entertain  Berzelius  in  1812  (29). 
Since  Berzelius  understood  little  of  what  the  English  chemists  were 
saying,  he  had  a  dull  time  at  Hatchett's  dinner  party.  It  was 
there  nevertheless,  that  he  first  made  the  acquaintance  of  Dr.  Alexandre 

Marcet 

In  his  travel  diary  Berzelius  wrote,  "Hatchett  himself  is  a  very  agree 
able  man  of  about  forty  to  forty-five  years.  His  father  was  a  rich  coach- 
maker,  and  the  son,  although  a  famous  chemist  at  the  time  of  his  father's 
death,  has  continued  to  carry  on  the  business.  He  is  in  very  good 
circumstances,  and  lives  in  Roehampton  on  a  little  estate  built  in  a  fine 
Italian  style  and  excellently  maintained.  .  .  .  Close  by  his  Italian  villa 
he  has  a  very  well-equipped  laboratory,  but  for  a  long  time  he  has  not 

worked"  (30). 

When  the  English  translation  of  Berzelius'  treatise  on  the  composi 
tion  of  animal  fluids  appeared,  Dr.  Marcet  wrote,  "Your  great  memoir  is 
an  honour  to  us.  Hatchett,  however,  complains  that,  when  you  hunted  in 
his  grounds,  you  didn't  even  cite  him;  but  I  have  explained  to  him,  as 
best  I  could,  the  haste  in  which  you  found  yourself  and  your  necessity 
of  abstaining  from  reference  work/' 

"I  am  very  sorry/'  replied  Berzelius,  ".  .  .  .  but  if  you  take  this  matter 
up  with  him  again,  tell  him  that  I  am  absolutely  ignorant  of  any  work 
of  his  on  these  subjects  other  than  that  of  the  testaceae.  .  .  "  Berzelius 
also  explained  that  he  had  confined  himself  almost  entirely  to  a  description 
of  his  own  work.  Dr.  Marcet  replied,  "I  gave  your  little  compliment  to 
Hatchett,  who  seemed  entirely  satisfied  with  it,  and  sends  you  his  best 
regards.  You  will  see  on  consulting  Thomson  [Thomas  Thomson,  "A 


386  DISCOVERY  OF  THE  ELEMENTS 

system  of  chemistry,"  1810]  that  he  has  written  more  than  once  on  animal 
substances"  (29). 

In  1813  Hatchett  published  in  the  Annals  of  Philosophy  a  method 
of  separating  iron  and  manganese  (31).  This  paper  was  in  the  form  of 
a  letter  to  Thomas  Thomson,  the  editor,  and  was  dated  "Mount  Clare, 
Roehampton,  Sept.  25,  1813."  A.  F.  Gehlen  had  used  succinic  acid  to 
separate  these  two  metals,  Professor  J.  F.  John  had  used  oxalic  acid,  but 
Hatchett  simply  precipitated  the  ferric  hydroxide  from  a  neutral 
solution  containing  ammonium  chloride,  leaving  the  manganese  in  solu- 

tion. 

In  1817  he  described  a  method  of  renovating  musty  "corn"  [wheat] 
by  floating  off  the  damaged  grain  with  boiling  water  and  carefully  drying 
the  rest  (32). 

In  his  history  of  Chelsea  (33),  Thomas  Faulkner  has  leftji  contempo 
rary  description  of  Hatchett's  fine  home,  Belle  Vue  House.  "This  capital 
mansion,"  says  Faulkner,  "was  built  by  Mr.  Hatchett's  father  in  1771; 
and  the  weeping  willow  opposite  to  the  house,  reckoned  one  of  the  finest 
trees  of  its  kind  in  England,  was  planted  by  him  in  1776;  it  commands 
beautiful  views  of  the  Thames  and  the  distant  Surrey  Hills."  In  the 
house  were  paintings  by  several  great  masters,  a  portrait  of  Mrs.  Hatchett 
by  Gainsborough,  a  large  organ,  a  collection  of  manuscript  and  printed 
music,  and  some  Mongol  idols  coUected  by  Hatchett's  friend  Peter  Simon 
Pallas,  the  famous  traveler.  "The  Library,"  said  Faulkner,  "is  extensive, 
and  contains  many  valuable  editions  of  the  Greek  and  Latin  Classics, 
together  with  a  numerous  series  of  Historical  Works,  and  the  voluminous 
Transactions  and  Memoirs  of  the  Royal  Society  -and  other  similar  learned 
Institutions  of  Europe." 

In  December,  1818,  Dr.  Marcet  wrote  to  Berzelius,  "Wollaston,  [Sir 
William]  Congreve,  and  Hatchett  are  hard  at  work,  but  up  to  the  pres 
ent  haven't  produced  anything."  Three  years  later  he  wrote:  "Hatchett  is 
taking  care  of  his  money  and  paying  court  to  personages  with  grand  titles; 
but  is  no  longer  doing  anything  in  chemistry,  and  I  do  not  even  know  that 
he  is  showing  much  interest  in  what  others  are  doing"  (29).  He  must 
have  retained  some  interest,  however,  for  on  September  15,  1823,  he 
was  elected  as  a  correspondent  for  the  chemical  section  of  the  AcadSmie 
des  Sciences.  In  1836  Hatchett  published  a  quarto  brochure  on  "The 
spikenard  of  the  ancients."  He  died  at  his  home,  Belle  Vue  House, 
Chelsea,  on  February  10,  1847,  at  the  age  of  eighty-two  years. 

In  1821  the  Reverend  J.  J.  Conybeare  (1779-1824)  named  an  Aus 
tralian  mineral  in  honor  of  "the  eminent  chemist  to  whom  we  are  in 
debted  for  the  most  valuable  contributions  towards  the  history  -and 
analysis  of  this  class  of  mineral  substances";  this  form  of  mineral  tallow 
is  still  known  as  hatchettine  or  hatchetttte.  He  found  later,  however,  that 


CONTRIBUTIONS  OF  CHARLES  HATCHETT  387 

it  was  identical  with  the  substance  W.  T.  Brande  had  referred  to  as 
mineral  adipocere  (34). 

In  1877  the  American  mineralogical  chemist  J.  Lawrence  Smith 
named  a  mineral  from  North  Carolina,  a  columbate  of  uranium,  hatchetto- 
lite,  because  Hatchett's  discovery  of  columbium  (niobium)  "was  clear, 
precise,  and  well  made  out,  and  has  never  been  controverted"  (35). 

The  author  wishes  to  thank  Dr.  C.  A.  Browne  and  Mr.  Allyn  B. 
Forbes  for  kindly  placing  at  her  disposal  their  correspondence  on  the 
history  of  columbite,  and  Mrs.  Gertrude  D.  Hess  for  examining  the 
papers  which  Thomas  P.  Smith  bequeathed  to  the  American  Philosophi 
cal  Society. 

LITERATURE  CITED 

(1)  STEPHEN,  LESLIE  and  SIDNEY  LEE,  "Dictionary  of  National  Biography,"  Vol. 

25,  Smith,  Elder  and  Co.,  London,  1891,  p.  153.  Article  on  Hatchett  by 
Gordon  Goodwin. 

(2)  Anonymous  obituary  of  Charles  Hatchett,  Gentlemen s  Mag.,  n.  s.,  28,  214-5 

(Aug.-,  1847). 

(3)  FAULKNER,  THOMAS,  "A  Historical  and  Topographical  Description  of  Chelsea 

and  Its  Environs,"  Vol  1,  T.  Faulkner,  Chelsea,  1829,  pp.  89-92. 

(4)  HATCHETT,  CHARLES,  "An  analysis  of  the  Carinthian  molybdate  of  lead  .  .  .  ," 

Phil  Trans.,  86,  285-339  (1796). 

(5)  HATCHETT,  CHARLES,  "An  analysis  of  the  earthy  substance  from  New  South 

Wales,  called  sydneia,  or  terra  australis,?  ibid.,  88,  110-29  (1798);  Nichol 
son's  /.,  2,  72-80  (May,  1798). 

(6)  HATCHETT,  CHARLES,  "Analysis  of  the  water  of  the  Mere  of  Diss,"  Phil  Trans., 

88,  572-81  (1798);  Nicholsons  J.,  3,  80-4  (May,  1799). 

(7)  HOME,  Sm  EVERARD,  "Some  observations  on  the  structure  of  the  teeth  of 

graminivorous  quadrupeds  .  .  .  ,"  Phil  Trans.,  89,  243-7  (1799). 

(8)  HATCHETT,  CHARLES,  "Experiments  and  observations  on  shell  and  bone,"  Phil 

Trans.,  89,  315-34  (1799);  Nicholsons  /.,  3,  500-6  (Feb.,  1800);  ibid.,  3, 
529-34  (March,  1800). 

(9)  HATCHETT,  CHARLES,  "Chemical  experiments  on  zoophytes,"  Phil  Trans.,  90, 

327-402  (1800). 

(10)  DAVY,  Sm  H.,  "An  account  of  some  experiments  on  the  constituent  parts  of 

some  asfaringent  vegetables,"  Nicholsons  J.,  [2],  5,  259  (Aug.,  1803). 

(11)  EC-STOCK,  JOHN,  "Observations  and  experiments  for  the  purpose  of  ascertaining 

the  definite  characters  of  the  primary  animal  fluids  .  .  ."  Nicholsons  J.,  [2], 
11,  251,  254  (Aug.,  1805). 

(12)  HATCHETT,  CHARLES,  "An  analysis  of  a  mineral  substance  from  North  America 

containing  a  metal  hitherto  unknown,"  Phil.  Trans.,  92,  49-66  ( 1802 ) .  Read 
Nov.  26,  1801.  Nicholsons  J.,  [2],  1,  32-4  (Jan.,  1802). 

(13)  HATCHETT,  CHARLES,  "Experiments  and  observations  on  the  various  alloys,  the 

specific  gravity,  and  on  the  comparative  wear  of  gold,"  Phil  Trans.,  93,  43- 
194  (1803);  Nicholson's  J.,  [2],  5,  286-303  (Aug.,  1803);  ibid.,  [2],  6,  145- 
61  (Nov.,  1803). 

(14)  HATCHETT,  CHARLES  "Analysis  of  a  triple  sulphuret  of  lead,  antimony  and 

copper  from  Cornwall,"  Phil  Trans.,  94,  63-9  (1804). 

( 15 )  SMITHSON,  JAMES,  "On  the  composition  of  trie  compound  sulphuret  from  Huel 

Boys  .  .  .  ,"  Nicholsons  J.,  [2],  20,  332-3  (SuppL,  1808). 


388  DISCOVERY  OF  THE  ELEMENTS 

(16)  HATCHETT,  CHARLES,  "Analytical  experiments  and  observations  on  lac,"  Phil 

Trans.,  94,  191-218  (1804);  Nicholsons  }.,  [2],  10,  45-55  (Jan.,  1805), 
ibid.,  [2],  10,  95-102  (Feb.,  1805). 

(17)  HATCHETT,  CHARLES,  "An  analysis  of  the  magnetical  pyrites;  with  remarks  on 

some  of  the  other  sulphurets  of  iron,"  Phil  Trans.,  94,  315-45  (1804); 
Nicholsons  J.,  [2],  10,  265-76  (Apr.,  1805);  ibid.,  [2],  11,  6-17  (May, 
1805). 

(18)  HATCHETT,  CHARLES,  "Observations  on  the  change  of  some  of  the  proximate 

principles  of  vegetables  into  bitumen;  with  analytical  experiments  on  a 
peculiar  substance  which  is  found  with  the  Bovey  coal,"  Phil.  Trans.,  94, 
385-410  (1804);  Nicholsons  /.,  [2],  10,  181-200  (March,  1805);  ibid.,  2, 
248-53  (Sept,  1798). 

(19)  HALL,  SIR  JAMES,  "Account  of  a  series  of  experiments  showing  the  effects  of 

compression  in  modifying  the  effects  of  heat,"  Nicholsons  J.,  [2],  14,  118 
(June,  1806);  ibid.,  [2],  14,  201-2  (July,  1806). 

(20)  NUGENT,  NICHOLAS,  "Account  of  the  Pitch  Lake  of  the  Island  of  Trinidad," 

ibid.,  [2],  32,  209  (July,  1812). 

( 21 )  HATCHETT,  CHARLES,  "On  an  artificial  substance  which  possesses  the  principal 

characteristic  properties  of  tannin,"  Phil.  Trans.,  95,  211-24,  285-315 
(1805);  ibid.,  96,  109-46  (1806);  Nicholsons  J.,  [2],  12,  327-31  (SuppL, 
1805);  ibid.,  [2],  13,  23-36  (Jan.,  1806);  ibid.,  [2],  15,  15-31  (Sept., 
1806);  ibid.,  [2],  15,  86-98  (Oct.,  1806). 

(22)  CHEVREUL,  M.  E.,  "Tanning  substances  formed  by  the  action  of  nitric  acid  on 

several  vegetable  matters,"  Nicholsons  J.,  [2],  32,  360-74  (SuppL,  1812); 
Ann.  chim.  pht/s.,  [1],  73,  36-66  (1810). 

(23)  WOLESENSKY,  EDWARD,  "Investigation  of  synthetic  tanning  material,"  Bureau 

of  Standards  Technologic  Paper  No.  302  (1925),  pp.  6-7. 

(24)  THOMSON,   THOMAS,   "A   System   of  Chemistry,"  4th   ed.,   Vol.   5,    Bell  and 

Bradfute,  Edinburgh,  1810,  p.  180. 

(25)  BOSWELL,  JAMES,  "Life  of  Samuel  Johnson,  LL.D.,"  Vol.  2,  edited  by  J.  W. 

Croker,  George  Bell  and  Sons,  London,  1876,  pp.  325-9. 

(26)  HOLMES,  TIMOTHY,  "Sir  Benjamin  Collins  Brodie,"  T.  Fisher  Unwin,  London, 

1898,  pp.  46  and  61-2. 

(27)  Anonymous  obituary  of  W.  T.  Brande,  /•  Chem.  Soc.  (London),  19,  509-11 

(1866). 

(28)  HAWKINS,  CHARLES,  "The  Works  of  Sir  Benjamin  Collins  Brodie,  with  an  Auto 

biography,"  Vol.  1,  Longman,  Green,  Longman,  Roberts,  and  Green,  London, 
1865,  pp.  55-8. 

(29)  SODERBAUM,  H.  G.,  "Jac.  Berzelius  Bref,"  Vol.  1,  part  1,  Almqvist  &  Wiksells, 

Upsala,  1912-1914,  p.  42.  Berzelius  to  Berthollet,  Oct.,  1812;  ibid.,  Vol.  1, 
part  3,  p.  19.  Marcet  to  Berzelius,  Jan.  25,  1813;  ibid.,  p.  45.  Marcet  to 
Berzelius,  May  5,  1813;  ibid.,  p.  58.  Berzelius  to  Marcet,  June  30,  1813; 
ibid.,  p.  66.  Marcet  to  Berzelius,  July  28  and  Aug.  4,  1813;  ibid.,  p.  183. 
Marcet  to  Berzelius,  Dec.,  1818;  ibid.,  pp.  231-2.  Marcet  to  Berzelius,  Jan. 
15,  1822. 

(SO)     BERZELIUS,  J.  J.,  "Reseanteckningar,"  P.  A.  Norstedt  &  Soner,  Stockholm,  1903, 
pp.  23-4,  29,  and  38. 

( 31 )  HATCHETT,  CHARLES,  "On  the  method  of  separating  iron  from  manganese," 

Annals  of  Philos.,  2,  343-5  (Nov.,  1813);  J.  F.  JOHN,  ibid.,  2,  172-3  (Sept., 
1813). 

(32)  HATCHETT,  CHARLES,  "A  description  of  a  process  by  which  corn  tainted  with 

must  may  be  completely  purified,"  Phil.  Trans.,  107,  36-8  (1817).  Letter 
to  Sir  Joseph  Banks. 

(33)  FAULKNER,  THOMAS,  "A  Historical  and  Topographical  Description  of  Chelsea 

and  its  Environs/'  Vol.  1,  T.  Faulkner,  Chelsea,  1829,  pp.  89-92. 

(34)  CONYBEARE,  J.  J.,  "Description  of  a  new  substance  found  in  ironstone,"  Annals 

of  Philos.,  17,  136  (Feb.,  1821);  ibid.,  21,  190  (March,  1823). 


CONTRIBUTIONS  OF  CHABLES  HATCHETT     389 

(35)  SMITH,  J.  LAWRENCE,  "Examination  of  American  minerals.    No.  6— Description 

of  columbic  acid  minerals  from  new  localities  in  the  United  States,  embrac 
ing  a  reclamation  for  the  restoration  of  the  name  columbium  to  the  element 
now  called  niobium  .  .  .  ,"  Am.  /.  Sci.,  [3],  13,  359-69  (May,  1877). 

(36)  "New  American  metal,"  Medical  Repository,  6,  212  (Aug.,  Sept.,  Oct.,  1802); 

"Hatchett's  analysis  of  the  American  mineral  substance  containing  a  metal 
hitherto  unknown,"  ibid.,  6,  323-4  (Nov.,  Dec.,  1802,  Jan.,  1803). 

(37)  "Place  where  the  ore  of  columbium  was  found,"  ibid.  (2),  2,  437  (Feb.,  Mar., 

Apr.,  1805). 

(38)  MILLIN,  A.-L.,  "Nouvelles  litteraires.  Etats-Unis  d'Amerique,"  Magasin  En- 

cyclopedique,  6,  388-9  (1805). 

(39)  "Selections  from  an  ancient  catalogue  of  objects  of  natural  history,  formed  in 

New  England  more  than  one  hundred  years  ago  by  John  Winthrop,  F.  R.  S.," 
Am.  J.  Sci.  ( 1 ) ,  47,  282-90  ( 1844 ) ;  Journal  Book  of  the  Roy.  Soc.?  15,  451- 
87  (June  27,  1734). 

(40)  SWEET,  JESSIE  M.}  "Sir  Hans  Sloane:     Life  and  mineral  collection,"  Natural 

History  Mag.,  5,  115-6  (July,  1935). 

(41)  "A  report  on  the  Geological  Survey  of  the  state  of  Connecticut  by  Professor 

Charles  Upham  Shepard,  M.D.,  .  .  .  with  extracts  and  remarks  by  the  editor 
[B.  Silliman],"  Am,  /.  Sci.  (1),  33,  162-3  (1838). 

(42)  SMITH,  EDGAR  F.,  "Chemistry  in  Old  Philadelphia,"  J.  B.  Lippincott  Co.,  Phila 

delphia,  1919,  pp.  14-22. 
(48)     "New  metal  columbium,"  Nicholsons  J.,  14,  181  (June,  1806). 

(44)  BROWNE.  C.  A.,  "Scientific  notes  from  the  books  and  letters  of  John  Winthrop 

Jr.  (1606-1676),  first  governor  of  Connecticut,"  Isis,  11,  325-42  (1928). 

(45)  Letter  of  Allyn  B.  Forbes  to  C.  A.  Browne,  Apr.  5,  1940.    Quoted  by  permis 

sion. 

(46)  "Collections  of  the  Massachusetts  Historical  Society,"  series  5,  Vol.  8,  Boston, 

1882,  pp.  126-7, 

(47)  SMITH,  EDGAR  F.,  "Chemistry  in  America,"  D.  Appleton  and  Co.,  New  York 

and  London,  1914,  p.  36. 

(48)  WEEKS,  M.  E.  and  L.  0.  AMBERG,  "M.-E.  Chevreul.    The  fiftieth  anniversary 

of  his  death,"  J.  Am.  Pharm.  Assoc.,  Sci.  Ed.,  29,  89-96  (Feb.,  1940). 

(49)  LEMAY,  PIERRE  and  R.  E.  OESPER,  "Michel  Eugene  Chevreul  (1786-1889)," 

/.  Chem.  Educ.,  25,  62-70  (Feb.,  1948). 

(50)  HALL,  C.  R.,  "A  chemist  of  a  century  ago,"  ibid.,  5,  253-7  (Mar.,  1928) 

(Samuel  L.  Mitdbill.) 

(51 )  SWADSE,  D.  J.,  "Samuel  Johnson's  interest  in  scientific  affairs,"  J.  Chem.  Educ., 

25,  458-9  (Aug.,  1948). 

(52)  SARTON,  GEORGE,  "Hoefer  and  Chevreul  (with  an  excursus  on  creative  cen 

tenarians),"  Bull  History  of  Medicine,  8,  419-45  (Mar.,  1940). 

(53)  MILES,  WYNDHAM,  "Thomas  Peters  Smith.    A  typical  early  American  chemist, 

/.  Chem.  Educ.,  30, 184-8  (Apr.  1953). 

(54)  HALL,  C.  R.,  "A  Scientist  in  the  Early  Republic.     Samuel  Latham  Mitchill, 

1764-1831,"  Columbia  University  Press,  New  York,  1939,  162  pp. 


From  J.  Hoffner's  "Schloss  Tegel" 

Baron  Alexander  von  Humboldt,  1769-1859.  German  naturalist  and  trav 
eler.  His  "Narrative  of  Travels  to  the  Equinoctial  Regions  of  America 
between  1799  and  1844"  and  his  "Political  Essay  on  the  Kingdom  of  New 
Spain"  are  a  rich  source  of  information  on  the  history  of  chemistry  in  Latin 
America.  He  introduced  the  Peruvian  fertilizer  guano  to  European  agri 
cultural  chemists.  Because  of  the  breadth  of  his  interests  he  had  an  unusually 
clear  understanding  of  the  interrelationships  of  the  various  branches  of 


Contributions  of  Andres  Manuel  del  Rio* 


Although  A.  M.  del  Rio,  the  eminent  discoverer  of  the  element 
now  known  as  vanadium,  spent  most  of  his  active  life  in  Mexico 
and  a  few  years  in  Philadelphia,  his  services  to  chemistry  and 
mineralogy  are  not  as  widely  known  and  appreciated  by  American 
scientists  as  they  deserve  to  be.  He  was  a  schoolmate  and 
honored  friend  of  Baron  Alexander  von  Humboldt  and  a  worthy 
colleague  of  Don  Fausto  de  Elhuyar,  first  director  of  the  School 
of  Mines  of  Mexico. 


Lndres  Manuel  del  Rio  y  Fernandez  was  born  on  Ave  Maria 
Street  in  Madrid  on  November  10,  1764,1"  and  received  his  preliminary 
training  at  the  College  of  San  Isidro.  At  the  age  of  fifteen  years  he  com 
pleted  his  courses  in  Latin,  Greek,  literature,  and  theology  and  received 
his  Bachelor's  degree  from  the  famous  University  of  Alcala  de  Henares, 
which,  two  centuries  before,  had  rivaled  Salamanca.  When  Don  Jose 
Solano  held  a  public  contest  in  experimental  physics,  the  young  graduate 
in  theology  distinguished  himself  so  highly  that  the  King  provided  for 
his  further  education  at  the  Mining  Academy  of  Almaden.  Because  of 
del  Rio's  enthusiasm  for  mining  and  subterranean  geometry,  the  Minister 
of  the  Indies,  Don  Diego  Gardoqui,  selected  him  to  study  in  France, 
England,  and  Germany  at  government  expense  (1). 

He  studied  chemistry  in  Paris  under  Jean  Darcet  and  attended 
lectures  in  medicine  and  natural  history.  In  1789  he  enrolled  at  the 
Royal  School  of  Mines  in  Freiberg,  Saxony,  where  great  things  were  ex 
pected  of  him  because  of  the  enviable  records  made  previously  by  his 
fellow  countrymen  Don  Juan  Jose  and  Don  Fausto  de  Elhuyar.  He,  too, 
soon  felt  the  charm  of  A.  G.  Werner's  teaching  of  geognosy  and  miner 
alogy.  One  of  del  Rio's  intimate  friends  at  the  Freiberg  Academy  was  his 
schoolmate,  Baron  Alexander  von  Humboldt,  who  later  renewed  the 
friendship  in  Mexico.  Del  Rio  also  studied  subterranean  geometry, 

*  Presented  before  the  Division  of  History  of  Chemistry  at  the  Cleveland  meeting  of 
the  A.  C,  S.,  Sept  11,  1934. 

t  Although  the  year  of  del  Rio's  birth  has  frequently  been  given  as  1765,  Ramirez 
(Ref.  1)  obtained  the  above  date  from  the  birth  certificate. 

391 


392  DISCOVEKY  OF  THE  ELEMENTS 

analytical  chemistry,  and  metallurgy  at  the  Royal  School  of  Mining  and 
Forestry  at  Schemnitz,  Hungary  ( Stiavnica  Banska,  Czechoslovakia ) . 

In  1791  Senor  del  Rio  visited  the  metallurgical  industries  of  England. 
During  a  second  sojourn  in  France,  he  was  associated  with  Lavoisier,  and 
in  the  troublous  days  of  1793,  he,  too,  almost  fell  prey  to  the  fury  of  the 
revolutionists.  According  to  Ramirez  (1),  del  Rio  disguised  himself  as 
a  water  carrier  and  escaped  to  England.  Although  offered  the  director 
ships  of  several  mining  enterprises,  he  declined  them. 

In  1793  a  royal  order  decreed  that  Werner's  theory  of  the  formation 
of  veins  be  taught  at  the  School  of  Mines  of  Mexico  recently  founded  by 
Don  Fausto  de  Elhuyar  (2).  The  professorship  of  mineralogy  was 
therefore  offered  to  Senor  del  Rio,  who  had  previously  declined  that 
of  chemistry.  Early  in  August,  1794,  he  set  sail  from  Cadiz  on  the  warship 
San  Pedro  Alcantara,  taking  with  him  a  servant  and  a  supply  of  apparatus 
for  the  School  of  Mines.  Eleven  weeks  later  he  disembarked  at  Vera 
Cruz  (3). 

After  arriving  at  Mexico  City,  del  Rio  immediately  arranged  the 
mineral  collections  and  planned  his  course  in  oryctognosy,  which  in 
cluded  mineralogy,  geognosy,  and  paleontology  and  which  began  on 
April  27,  1795.  The  new  world  spread  forth  before  him  so  many  objects 
of  scientific  inquiry  that  he  afterward  wrote  with  enthusiasm:  "Each  step 
of  the  traveler  in  this  Republic  discovers  to  him  something  new"  (4). 

In  1795  he  published  the  first  edition  of  his  "Elements  of  Oryctognosy" 
(5),  which  von  Humboldt  regarded  as  "the  best  mineralogical  work 
which  Spanish  literature  possesses"  (6),  and  which  Santiago  Ramirez  (7) 
called  "a  monumental  work,  which  .  .  .  will  be  an  object  of  veneration  and 
consultation  by  the  mineralogists  of  our  country  and  for  all  those  who 
.  .  .  are  occupied  in  studying  the  mineralogy  of  our  native  country/* 

Del  Bio's  paper  on  the  best  method  of  sinking  mine  shafts  was 
printed  for  use  in  ah1  the  mines  of  Mexico,  and  his  article  on  the  relations 
between  the  composition  of  a  mineral  and  the  materials  of  which  the  vein 
is  composed  was  published  in  the  supplement  to  the  Gaceta  de  Mexico 
on  January  18,  1797  (1,3). 

The  most  outstanding  achievement  of  del  Rio's  long,  useful  life  was 
his  discovery  in  1801  of  the  metal  now  known  as  vanadium.  He  found 
that  the  brown  lead  mineral,  Plomo  par  do  de  Zimapdn  (8),  from  the 


Enrique  Moles,  1883-1953.  Distinguished  Spanish  chemist  and  pharmacist. 
Professor  of  Inorganic  and  Physical  Chemistry  in  the  Faculty  of  Chemical  Sciences 
at  Madrid.  His  papers  on  non-aqueous  solutions,  molecular  volumes  and  addi- 
tivity,  inorganic  complexes,  and  atomfe  weight  determinations  were  published  in 
the  leading  journals  of  Spain,  England,  France,  Italy,  and  the  Netherlands.  See 

alsoref.  (31). 


CONTRIBUTIONS  OF  ANDRES  MANUEL  DEL  RIO  393 


Courtesy  R.  E.  Oesper 


394  DISCOVERY  OF  THE  ELEMENTS 

Cardonal  Mine  in  Hidalgo  contained  what  he  believed  to  be  a  new  metal. 
Because  its  salts  are  of  varied  colors,  he  at  first  called  it  panchromium, 
but  because  its  salts  with  alkalies  and  earths  become  red  on  heating  or 
on  treatment  with  acids,  he  later  changed  the  name  to  erythronium 

(1,  9,  10). 

When  von  Humboldt  visited  Mexico  in  1803,  del  Rio  gave  him 
several  specimens  of  the  brown  lead  ore.  Von  Humboldt  sent  some  of 
them  to  the  Institut  de  France  with  an  explanatory  letter  giving  del  Rio's 
analysis  and  his  conclusions  regarding  the  close  resemblance  of  the  new 
metal  to  chromium  and  uranium.  A  more  detailed  description  addressed 
to  Chaptal  was  lost  in  a  shipwreck  (10). 

Since  the  properties  of  erythronium  closely  resembled  those  which 
Fourcroy  had  ascribed  to  the  recently  discovered  metal  chromium,  del 
Rio  lost  confidence  in  the  importance  of  his  discovery  and  concluded 
that  his  supposed  new  element  was,  after  all,  nothing  but  chromium  (11). 
In  a  note  to  his  translation  of  Karsten's  "Mineralogical  Tables"  he  wrote 
(7,  9,  12):  ".  .  .  but,  knowing  that  chromiurn  also  gives  by  evaporation 
red  or  yellow  salts,  I  believe  that  the  brown  lead  is  a  yellow  oxide  of  chro 
mium,  combined  with  excess  lead  also  in  the  form  of  the  yellow  oxide." 

Dr.  Ernst  Wittich,  German  Ambassador  to  Mexico,  pointed  out  that 
Baron  von  Humboldt  was  also  led  into  the  same  error,  for  the  specimen 
in  the  Museum  fur  Naturkunde  in  Berlin  is  labeled  in  the  Baron's  hand 
writing:  "Brown  lead  ore  from  the  veins  of  Zimapan  in  northern  Mexico. 
Lead  chromate.  M.  del  Rio  thought  he  had  discovered  a  new  metal  in  it, 
which  he  named  erythronium,  then  panchromium;  later  he  realized  that 
it  was  ordinary  chromium."  The  label  was  later  corrected  by  Gustav 
Rose  to  read:  "Vanadiumbleierz"  (vanadium  lead  ore)  (29). 

Another  circumstance  which  helped  to  shake  del  Rio's  confidence  in 
his  own  work  was  the  analysis  of  this  mineral  which  H.-V.  Collet- 
Descotils,  a  friend  of  VauqueHn,  published  in  1805  (13).  When  Collet- 
Descotils  concluded  that  the  supposed  new  metal  was  merely  chromium, 
del  Rio  warmly  defended  his  own  prior  claim  to  the  "discovery"  of 
chromium  in  the  brown  lead  ore  (14). 

The  details  of  N.  G.  Sefstrom's  discovery  of  vanadium  in  soft  iron 
from  the  Taberg  Mine  in  Smaland,  Sweden,  and  of  F.  Wohler's  proof  of 
the  identity  of  erythronium  and  vanadium  have  already  been  related  (14, 
IS,  16).  Dr.  Enrique  Moles  emphasized  the  fact  that  del  Rio's  own 
excessive  modesty  and  scientific  caution  led  him  to  renounce  the  dis 
covery  of  the  new  element  before  the  analysis  of  Collet-Descotils  had 
been  published. 

Unaware  of  the  shipwreck  which  had  prevented  Humboldt  from 
giving  full  publicity  to  the  discovery  of  erythronium,  del  Rio  wrote  in 


CONTRIBUTIONS      OF  ANDKES   MANUEL   DEL  RIO  395 


ELEMENTOS 


ORICTOGNOSIA, 

6    DEL, 

CONOCIMIENTO  DE  IX>S  FOSILES, 

SEGUN  EL  SISTEMrf  DE  BERCELIQJ 

\  Y    SEOT7N    JLOS 

'RINCIPIOS  DE  ABRAHAM  GOTTLOB  WERNER. 

CON  LA 


,^  _.,0 af  JZlemana   y 

^ 


PARA  USO  DEI, 

SEMINARIO  NACIONAL  DE  MINERIA 

DE  MEXICO. 


Por  el  C.  ANDRES  DEL  RIO* 

*  PlCbFESOR  DE  MINERALOGIA  DEX.  MISMO  Y  SOCIO  Y  CORRESPONSAI. 
DE  AJMJUNAS  ACADEMIAS    NACIOKALES  Y  ESTRANGERA6. 


PARTE  PRACTICA  —  SEGUNDA  EDICIO1S? 


IMPRENTA  DE  JUAN  F.  HURTEI.. 
1833. 


Courtesy  Am,  Philosophical  Soc. 

Title  Page  of  del  Rio's  "Elements  of  Oryctognosy"  written 

according  to  the  system  of  Berzelius  and  the  principles  of 

A.  G.  Werner 


396  DISCOVERY  OF  THE  ELEMENTS 

1832  in  his  "Elements  of  Oryctognosy":  "When  he  left  Mexico,  I  gave  him 
...  a  copy  in  French  of  my  experiments  in  order  that  he  might  publish 
them.  If  he  had  judged  them  worthy  of  public  attention,  they  would 
have  excited  the  curiosity  of  chemists,  and  the  discovery  of  the  new  metal 
would  not  have  been  delayed  for  thirty  years,  which  is  the  objection  now 
unjustly  made  against  me.  He  did  not  even  show  Descotils  the  copy 
of  my  experiments,  for,  since  he  [Descotils]  was  a  chemist,  he  would 
have  appreciated  them  better,  would  have  repeated  them,  and  with  his 
knowledge  of  chromium,  which  I  lacked,  it  would  have  been  easy  for 
him  to  decide  that  it  was  a  distinct  metal"  (7,  17).  Since  at  that  time 
chromium  must  have  been  a  novelty  even  in  Europe  and  since  it  often 
required  ten  or  twelve  years  for  the  news  of  European  discoveries  to 
reach  Mexico  (22),  del  Rio  should  not  be  criticized  for  having  been 
uninformed  as  to  the  properties  of  this  metal. 

For  a  number  of  years  del  Rio  taught  not  only  mineralogy  and 
mining,  but  also  Spanish  and  French,  and  served  as  one  of  the  editors 
of  the  Gaceta  de  Mexico,  to  which  he  contributed  many  articles,  both 
literary  and  scientific.  In  order  that  his  students  might  "be  proud  of  a 
country  that  offers  so  many  opportunities  for  admiring  Nature,"  del  Rio 
added  to  his  translation  of  Karsten's  "Mineralogical  Tables"  a  number  of 
descriptions  of  minerals  from  "this  America"  and  "the  other  America." 
Since  a  French  reviewer  (5)  had  criticized  him  in  1797  for  not  completely 
adopting  the  new  nomenclature  proposed  by  Lavoisier,  del  Rio  wrote  in 
1804,  "Usage  has  accepted  oxigeno  in  place  of  arcicayo,  oxido  in  place  of 
cayo  .  .  .  and  I  have  adjusted  the  nomenclature  in  conformity  with  it" 
(9).  In  1805  he  published  the  second  volume  of  his  "Elements  of 
Oryctognosy." 

In  1809  he  established  at  Coalcoman,  Michoacan,  the  first  ironworks 
in  Mexico,  which,  however,  were  destroyed  during  the  insurrection  of 
1811  (1,  3).  An  incident  related  by  Ramirez  (1)  illustrates  the  fairness 
of  del  Rio's  judgment.  When  the  master  blacksmith  at  the  Coalcoman 
ironworks,  who  regarded  his  own  skill  as  superior  to  that  of  del  Rio, 
asked  for  the  use  of  an  experimental  furnace,  del  Rio  granted  the  request. 
Although  the  experiments  resulted  disastrously,  del  Rio's  report  merely 
stated:  "Pillado  did  not  succeed  very  well,  but  these  are  the  first  experi 
ments." 

Von  Humboldt,  who  was  greatly  interested  in  del  Rio's  pumping 
engine,  described  it  as  follows:  "This  engine,  which  is  the  first  of  this  kind 
constructed  in  America,  is  much  superior  to  those  in  the  mines  of  Hungary; 
it  was  constructed  according  to  the  estimates  and  plans  of  Senor  del 
Rio,  professor  of  mineralogy  of  Mexico,  who  has  visited  the  most  famous 
mines  of  Europe  and  who  possesses  most  thorough  and  varied  erudition; 


CONTRIBUTIONS  OF  ANDRES  MANUEL  DEL  RIO  397 


/***' 

Courtesy  Am.   Philosophical   Soc. 


In  a  presentation  copy  of  his  translation  o£  Karsten's 
"Miner  alogical  Tables,"  del  Bio  wrote  as  follows:  "To 
the  Philosophical  Society  of  Philadelphia  this  work  is  most 
respectfully  dedicated,  which  contains  four  new  discov 
eries,  t?£s.—  the  sulphur  of  manganese,  acknowledged  by 
Mr.  Proust  to  have  been  discovered  by  me—  the  sous- 
chramate  of  lead,  the  analysis  of  which  is  contained  in 
these  tables,  and  was  published  in  the  Annales  of  Nat 
ural  Sciences  at  Madrid  as  a  discovery  of  mine  a  year 
before  that  of  Mr.  Des-Cotils  at  Paris—  the  hydrophanous 
copper  (the  Dioptase  of  Mr.  Haiiy),  which  contains  the 
same  principles  of  that  found  in  Siberia  and  analyzed 
by  Mr.  Lowitz,  cfe.,  silex,  water,  and  oxide  of  copper- 
also  the  lavender  bleu  copper  ore,  which  is  a  carbonate 
of  copper  and  silver  possessing  the  greatest  proportion 
of  the  former,  by  the  translator  Andre  del  Rio,  Mexico 
the  2,  June  1818." 


398  DISCOVERY  OF  THE  ELEMENTS 

and  Mr.  Lachaussee,  an  artisan  native  of  Brabant,  a  man  of  marked  ability, 
built  it.  ...  It  is  unfortunate  that  this  beautiful  engine,  whose  throttle 
valve  is  provided  with  a  special  mechanism,  is  set  up  in  a  place  where 
it  is  difficult  to  get  enough  water  to  run  it  continuously.  .  .  ."  The  Baron 
then  explained  that  the  amount  of  water  had  been  estimated  in  an 
unusually  rainy  year,  and  added  that  "Seflor  del  Rio,  when  he  arrived 
in  New  Spain,  had  no  other  aim  than  that  of  proving  to  Mexican  mine 
operators  the  effect  of  such  machines  and  the  possibility  of  making  them 
in  this  country  ..."  (6).  Ramirez  (1)  stated,  however,  that  del  Rio 
had  predicted  the  diminution  of  water  supply,  but  had  been  unable  to 
prevent  the  deforestation  which  had  caused  it. 

In  1820  deputies  were  appointed  to  the  Spanish  court.  H.  H.  Ban 
croft  stated  in  his  "History  of  Mexico"  that  this  election  "took  place  with 
no  little  disorder"  and  that  ".  .  .  the  choice  fell  almost  exclusively  on 
ecclesiastics  and  lawyers,  with  a  sprinkling  of  soldiers,  merchants,  and 
men  of  no  particular  calling,  among  whom  were  three  natives  of  Spain" 
(18).  One  of  the  latter  was  Andres  Manuel  del  Rio,  who  pleaded 
earnestly  for  the  independence  of  his  adopted  country.  Although  Elhuyar 
resigned  his  position  and  returned  to  Spain  during  the  struggle,  del  Rio 
was  in  sympathy  with  the  new  cause  (19}  and,  according  to  Maffei  and  de 
la  Rua  Figueroa  ( 1 ) ,  was  one  of  the  few  deputies  to  vote  for  absolute  inde 
pendence. 

During  his  visit  to  Spain,  del  Rio  was  offered  the  directorship  of  the 
mines  of  Almaden  and  of  the  Museum  of  Sciences  in  Madrid,  but  he 
preferred  to  return  to  Mexico.  While  he  was  in  Bordeaux,  Seiiora  de 
Elhuyar  said  to  him,  "Where  are  you  going,  del  Rio?  Don't  you  know 
that  Mexico  has  become  independent?"  "Yes,"  replied  del  Rio,  "and  I 
am  going  home  to  my  country"  (I).  Because  of  his  loyal  friends  and 
eager,  intelligent  students,  his  splendid  collection  of  minerals  from  both 
hemispheres,  the  undiscovered  wonders  of  the  new  world,  and  the  charm 
of  his  virtuous  Mexican  wife,  del  Rio  had  come  to  regard  Mexico  as  his 
homeland.  Perhaps  another  incentive  for  his  return  was  the  impressive 
structure  for  the  School  of  Mines  which  had  been  completed  in  1813, 
and  which  Mr.  Beulloch,  a  contemporary  English  traveler,  described  as 
follows  (20}: 

"The  edifice  in  which  it  is  located  excels  in  its  dimensions  and  in 
the  beauty  of  its  architecture  all  those  in  Europe  destined  for  the  same 
purpose.  It  was  erected  at  great  cost  [!1/2  million  pesos]  and  amply 
provided  with  everything  necessary  for  the  mine  owners  and  other  rich 
inhabitants."  Earthquakes  soon  damaged  the  noble  structure  to  such 
an  extent  that  by  1830  extensive  repairs  were  needed.  The  architect 
took  the  high  building  apart,  placed  the  stately  columns  in  the  patio,  and 
put  them  back  in  place  without  losing  a  single  piece  (7). 


CONTRIBUTIONS    OF    ANDRES    MANUEL    DEL    RIO 


399 


Courtesy  Dr.  Harold  Hibbert  of  McGill  University 

John  Dalton,  1766-1844.  English  Quaker  chemist.  Teacher 
of  mathematics  and  physics  at  New  College,  Manchester. 
In  his  "New  System  of  Chemistry"  he  showed  how  his 
atomic  theory  can  be  used  to  explain  the  laws  which  govern 
chemical  combination.  He  also  made  careful  meteorological 
observations  and  described  color-blindness  (daltonism). 
See  also  ref.  (32). 


400  DISCOVERY  OF  THE  ELEMENTS 

In  1824  del  Rio  published  an  analysis  of  a  gold-rhodium  alloy  from 
the  smelting  house  in  Mexico  which  was  similar  to  the  gold-palladium 
ingot  previously  reported  by  Joseph  Cloud,  director  of  the  Philadelphia 
Mint  (21).  Three  years  later  he  published  a  translation  of  Berzelius's 
"New  mineral  system"  (22).  He  served  for  some  time  on  a  committee 
appointed  to  inspect  the  money  and  improve  working  conditions  at  the 
Mint. 

In  acknowledgment  of  his  allegiance,  the  new  government,  which 
expelled  most  Spaniards  from  Mexico  in  1828,  made  an  exception  in  the 
case  of  del  Rio.  Nevertheless,  he  preferred  to  share  the  fate  of  his  fellow- 
countrymen  and  therefore  spent  four  years  of  voluntary  exile  in  Philadel 
phia.  In  the  preface  to  the  second  edition  of  his  "Elements  of  Oryctog- 
nosy,"  published  in  Philadelphia  in  1832  at  the  expense  of  the  Mining 
Tribunal  of  Mexico,  he  wrote: 

"Knowing  by  experience  the  happy  disposition  of  Mexican  youth  for 
the  study  of  these  sciences,  I  wish  in  the  last  third  of  my  life  to  conse 
crate  to  it  the  limited  product  of  my  efforts,  immeasurably  happy  if  I  can 
some  day  be  useful  to  a  country  where  I  have  lived  for  thirty-five  years, 
receiving  every  kind  of  distinction.  If  the  result  is  not  proportional  to  my 
high  aim,  it  will  at  least  be  admitted  that  I  aspire  to  manifest  in  the 
only  manner  possible  to  me  my  gratitude  for  the  distinguished  favors 
with  which  the  Mexicans  have  honored  me;  my  only  merit  is  to  be  thank 
ful"  (17). 

In  his  unassuming  devotion  to  his  teaching  duties,  del  Rio  resembled 
John  Dalton.  One  day  in  1841,  when  a  student  knocked  at  the  door  of 
his  classroom  to  announce  a  distinguished  visitor,  del  Rio  asked  the 
messenger  to  have  the  visitor  wait  for  him.  When  the  bell  rang  at  the 
close  of  the  class  period,  del  Rio  greeted  Senor  Calderon  de  la  Barca, 
minister  plenipotentiary  from  the  Court  at  Madrid.  His  Excellency, 
moreover,  was  not  offended  at  the  delay  (1 ). 

Del  Rio  belonged  to  many  scientific  organizations  of  France,  Ger 
many,  Great  Britain,  Mexico,  and  Spain,  and  was  an  active  member  of 
the  American  Philosophical  Society  and  president  of  the  Geological  So 
ciety  of  Philadelphia.  From  1830  to  1834  he  attended  the  meetings  of 
the  American  Philosophical  Society,  took  part  in  the  discussions,  donated 
books  which  are  still  in  possession  of  the  Society's  library,  and  presented 
papers  for  publication. 

The  translation  of  Karsten's  Tables  contains  in  del  Rio's  handwriting 
tihe  following  note  of  presentation:  "To  the  Philosophical  Society  of 
Philadelphia,  this  work  is  most  respectfully  dedicated,  which  contains 
four  new  discoveries— the  sulphur  of  manganese,  acknowledged  by  Mr. 
Proust  to  have  been  discovered  by  me— the  sous-chromate  of  lead  .  .  .  the 
hydrophanous  copper  .  .  .  also  the  lavender  .  .  .  copper  ore."  This  note 


CONTKDBUTTONS  OF  ANDRES  MANUEL  DEL  RIO  401 

was  written  in  1818,  but  in  1827  del  Rio  wrote:  "I  thank  Sr.  Breithaupt 
for  .  .  .  believing  me  the  first  discoverer  of  manganese  sulfide  ...  I  am 
indeed  [discoverer]  of  that  of  los  Mijes  in  the  state  of  Oajaca  [Oaxaca]; 
but  we  must  be  just.  Sr.  Proust  discovered  that  of  Transylvania  two  years 
before"  (22).  Del  Rio  added  that  at  that  time  many  European  dis 
coveries  were  not  known  in  Mexico  until  ten  or  twelve  years  after  publi- 

A  LA  MEMORIA  DEL  DISTINGUIDO  SABIO 


D.  ANDRES  MANUEL  DEL  RIO 


CUV*  MIKICIDA    TA 


ISTRODUCTOR  DE  LAS  CIENCIA8  NATERALE8 


KM  PCUTJU  P ATRIA 

CUYO  ACENDRADO  AMOK  A  MEXICO  LO  IIACE  FIGURAR  ENTRE 

NUESTROS   MAS   I  LUSTRES  COMPATRIOT  AS; 

Y     El*    CUYAS    OBRAS    CIENTIFICAS    HAN    BEBIBO    LA    INSTRUCCION  NUESTRAS 
GEXERACIONES  DE  MIXEROS, 


ESTE  INSIGftsTIFICASTTE  TBABAJO 

a  JUS  RJSPEICOS3  DE  SCS  ADJIDUDORES. 

Dedication  Page  of  "The  Mineral  Wealth  of  Mexico  and 
Its  Present  State  of  Development/'  which  S.  Ramirez 
wrote  for  the  New  Orleans  Exposition  of  1884.  Trans 
lation:  "To  the  memory  of  the  distinguished  scientist, 
expert  mine  operator,  and  celebrated  mineralogist,  D. 
Andres  Manuel  del  Rio,  whose  well  deserved  fame  desig 
nated  him  to  be  the  introducer  of  the  natural  sciences  into 
our  country,  whose  stainless  love  for  Mexico  makes  him 
figure  among  our  most  illustrious  fellow  citizens,  and 
from  whose  scientific  books  our  generations  of  mine 
operators  have  imbibed  instruction,  this  unimportant 
work  is  dedicated  as  a  tribute  by  the  most  respectful  of 
his  admirers." 

cation.  In  the  second  edition  of  his  "Elements  of  Oryctognosy,"  del  Rio 
wrote:  "In  a  work  such  as  this  little  can  be  called  one's  own:  only  a  few 
articles  belong  to  me,  such  as  the  manganese  sulfide  of  Oaxaca,  the 
brown  lead  of  Zimapan,  the  mercury  iodide  of  Casas  Viejas,  the  blue 
silver  of  Catorce,  and  the  zinc  selenide  of  Culebras"  (17). 

His  requests  for  a  small  specimen  of  "sulphuret  of  silver"  and  other 
minerals  for  analysis  were  granted  by  the  Philosophical  Society.    At  its 


402  DISCOVERY  OF  THE  ELEMENTS 

meetings  he  must  have  met  A.  D.  Bache,  F.  Bache,  Robert  Hare,  Joseph 
Henry,  G.  W.  Featherstonhaugh,  and  other  contemporary  American 
scientists.  Ramirez  (1)  mentions  a  process  of  purifying  mercury  which 
del  Rio  had  learned  from  Professor  Hare  of  Philadelphia. 

In  1830  del  Rio  read  a  paper  on  BecquereFs  method  of  reducing 
silver  ores  (23).  His  paper  (24)  on  the  crystals  developed  in  vermiculite 
by  heat  begins:  "A  pupil  of  the  celebrated  Werner,  I  have  always  been 
more  of  a  Neptunian  than  a  Plutonist,  notwithstanding  the  many  crystalli 
zations  produced  in  the  dry  way.  A  new  instance  which  has  come  under 
my  observation  in  the  crystals  of  vermiculite  has  contributed  materially 
to  change  my  opinions.  .  .  ." 

Dr.  Meigs  had  heated  a  specimen  of  vermiculite  in  a  candle  flame  and 
had  shown  del  Rio  the  worm-like  filaments  which  shoot  out  from  it. 
Under  the  blowpipe,  the  Mexican  scientist  obtained  from  it  oblique  prisms 
nearly  an  inch  long,  which  were  also  "crooked  and  worm-like."  Ver 
miculite  is  a  hydrous  silicate  generally  produced  by  alteration  of 
mica. 

Between  1835  and  1837  several  polemical  articles  by  del  Rio  and 
Charles  U.  Shepard,  the  well-known  American  mineralogist  and  collector 
of  meteorites,  appeared  in  the  American  Journal  of  Science  (25). 

In  1834  del  Rio  was  given  the  chair  of  geology  in  addition  to  that  of 
mineralogy.  Before  returning  to  Mexico,  he  purchased  for  the  Mining 
Seminary  a  splendid  collection  of  shells  and  fossils  collected  by  a  Polish 
naturalist  who  had  recently  died  in  Philadelphia.  In  1841  he  published 
a  manual  of  geology  describing  the  fossil  flora  and  fauna  of  the  various 
rocks,  with  special  emphasis  on  those  found  in  Mexico  ( 7,  26 ) .  Two  years 
later  del  Rio,  then  about  seventy-eight  years  of  age,  served  on  a  committee 
to  study  the  manufacture  of  porcelain  and  determine  whether  or  not  the 
raw  materials  were  available  in  the  Republic.  Their  report,  which  was 
highly  praised  by  the  Bureau  of  National  Industry,  was  published  in  El 
Siglo  XIX  on  May  10,  1843,  and  a  porcelain  works  was  established  at 
Puebla  (3). 

Two  years  later  del  Rio  was  still  serving  as  professor  of  mineralogy, 
but  in  the  following  year  he  asked  for  a  substitute  in  order  that  he  might 
complete  the  supplement  to  his  textbook,  which  was  to  include  discussions 
of  the  most  recent  discoveries  made  in  Europe  and  the  United  States. 
According  to  Senor  Ramirez  (7),  this  was  published  in  1849  (27).  In 
spite  of  failing  eyesight,  del  Rio  continued,  almost  to  the  close  of  his  life, 
to  contribute  to  the  literary  and  scientific  periodicals  of  Mexico,  yet  in 
spite  of  his  illustrious  services,  he  was  reduced  to  poverty  in  his  old  age 
(28).  On  March  23,  1849,  he  suffered  a  fatal  cerebral  attack. 

Del  Rio's  colleague,  Don  Joaquin  Velazquez  de  Leon,  said  in  his 
eulogy:  "I  still  seem  to  see  him  leaving  this  college  at  the  close  of  the 


CONTRIBUTIONS  OF  ANDRES  MANUEL  DEL  RIO  403 

day's  teaching,  with  his  book  under  his  arm  (for  he  used  to  say  that  the 
support  of  science  does  not  dishonor  anyone);  surrounded  at  the  doorway 
of  the  institution  by  the  unfortunate  and  the  destitute,  sharing  with  them 
his  meager  salary,  and  returning  to  aid  those  who  were  already  waiting 
for  him  at  the  doors  of  his  home"  (1).  In  1877  a  rich  mining  region  of 
Chihuahua  was  named  in  his  honor  the  Andres  del  Rio  canton,  with 
Batopilas  as  its  capital  (7). 

In  honor  of  del  Rio  on  the  occasion  of  the  centenary  of  his  death, 
Professor  Modesto  Bargallo  of  the  National  Polytechnic  Institute  of  Mex 
ico  City  published  an  interesting  detailed  description  of  a  copy  of  the 
"Elementos  de  Orictognosia"  (Part  1,  1795)  containing  many  corrections 
and  addenda  in  del  Rio's  handwriting  (30).  Professor  Bargallo  has  just 
published  a  handsomely  illustrated  volume  on  mining  and  metallurgy  in 
Spanish  America  during  the  Colonial  epoch  (33). 

It  is  a  pleasure  to  acknowledge  the  kind  assistance  of  Miss  Eva 
Armstrong  of  the  Edgar  Fahs  Smith  Memorial  Library,  the  library  of  the 
American  Philosophical  Society,  Dr.  E.  Moles  and  Senor  A.  de  Galvez- 
Canero  of  Madrid,  and  Dr.  F.  B.  Dains. 


LITERATURE  CITED 

(1)  MAFFEI,  E.  and  R.  R.  FIGUEROA,  "Apuntes  para  una  biblioteca  espafiola  de 

libros  ,  .  .  relatives  al  conocimiento  y  explotacion  de  las  riquezas  minerales," 
Imprenta  de  J.  M.  Lapuente,  Madrid,  1872,  2  vols.,  529  and  693  pp.;  J. 
VELAZQUEZ  DE  LEON,  "Elogio  funebre  del  Sr.  D.  Andres  del  Rio,"  Vol.  2,  El 
Album  Mexicano,  Imprenta  de  Cumplido,  Mexico,  1849,  pp.  219-25;  S. 
RAMIREZ,  "Biografia  del  Sr.  D.  Andres  Manuel  del  Rio/7  Boletin  de  la  Soc. 
Mexicana  de  Geografia  y  Estadistica,  [4],  2,  205-51  (1890). 

(2)  WEEKS,  M.  E.,  "The  scientific  contributions  of  the  de  Elhuyar  brothers,"  J. 

Chem.  Educ.,  11,  413-9  (July,  1934). 

(3)  RAMIREZ,  S.,  "Datos  para  la  historia  del  Colegio  de  Mineria,"  government 

publication  for  the  Alzate  Society,  Mexico,  1890,  494  pp. 

(4)  DEL  Rio,  A.  M.,  "Analysis  of  two  new  mineral  substances,  consisting  of  bi- 

seleniuret  of  zinc  and  seleniuret  of  mercury,  found  at  Culebras  in  Mexico," 
Phil  Mag.,  [2],  4,  113-5  (Aug.,  1828). 

(5)  DEL  Rio,  A.  M.,  "Elementos  de  orictognosia,"  Vol.  1,  Imprenta  de  Zuniga  y 

Ontiveros,  Mexico,  1795,  172  pp.;  ibid.,  1805,  Vol.  2,  200  pp.;  Vol.  1  re 
viewed  in  Ann.  chim.  phys.,  [1],  21,  221-4  (Feb.,  1797). 

(6)  VON  HUMBOLDT,  A.,  "Ensayo  politico  sobre  Nueva  Espana,"  3rd  ed.,  Vol.  1, 

Libreria  de  Lecointe,  Paris,  1836,  pp.  232,  236-8;  Vol.  3,  pp.  117-8. 

(7)  RAMIREZ,  S.,  "Noticia  historica  de  la  riqueza  minera  de  Mexico,"  Secretaria  de 

Fomento,  Mexico,  1884,  768  pp. 

(8)  "Zimapan,  the  Leadville  of  Mexico,"  Modern  Mexico,  13,  30-1  (Sept.,  1902). 

(9)  DEL  Rio,  A.  M.,  "Tablas  Mineralogicas  Dispuestas  segun  los  Descubrimientos 

Mas  Recientes  e  Ilustradas  con  Notas  por  D.  L.  G.  Karsten,"  Zuniga  y  Onti 
veros,  Mexico,  1804,  pp.  60-62;  RAMON  DE  LA  QUADRA,  "Introducci6n  a 


404  DISCOVERY  OF  THE  ELEMENTS 

las  tablas  comparativas  de  las  substancias  metalicas,"  Anales  ciencias  not- 
urales  ( Madrid ) ,  6,  46  ( May,  1803 ) . 

(10)  WITTICH,  E.,  "Zur  Entdeckungsgeschichte  des  Elementes  Vanadium,"  Technik- 

Industrie  und  Schweizer  Chem.-Ztg.,  16,  4-5  (Jan.  31,  1933). 

(11 )  DE  FOURCROY,  A.-F.,  "Systeme  des  connaissances  chimiques,"  Vol.  5,  Baudouin, 

Paris,  1800  (Brumaire,  an  IX),  pp.  107-13. 

(12)  DEL  Rio,  A.  M.,  "Discurso  de  las  vetas,"  Gaceta  de  Mexico,  Nov.  12,  1802; 

Anales  de  las  Ciencias  Maturates  (Madrid),  7,  31  (Feb.,  1804).  These 
references  taken  from  E.  MOLES,  Ref.  (15). 

(IS)  COLLET-DESCOTTLS,  H.  V.,  "Analyse  de  la  mine  brune  de  plomb  de  Zimapan, 
dans  le  royaume  du  Mexique,  envoyee  par  M.  Humboldt,  et  dans  laquelle 
M.  del  Rio  dit  avoir  decouvert  un  nouveau  metal/'  Ann.  chim.  phys.,  [1], 
53,  268-71  (1805);  J.  L.  GAY-LUSSAC,  "Biographical  account  of  Hippolyte- 
Victor  Collet-Descotils,"  Annals  of  Philosophy,  9?  417-21  ( 1817);  Ann.  chim. 
phys.,  [2],  4,  213  (Feb.,  1817). 

(14)  WITTICH,  E.,  "El  descubrimiento  del  vanadio,"  Boletin  Minero,  13,  4-15  (Jan., 

1922);  see  also  del  Rio's  autograph  letter  reproduced  on  page  397. 

(15)  MOLES,  E.,  "Wolframio,  no  tungsteno.    Vanadio  o  eritronio,"  Anales  soc.  espan. 

fis.  quim.,  [3],  26,  234-52  (June,  1928). 

(16)  WEEKS,  M.  E.,  "The  discovery  of  the  elements,"  J.  Chem.  Educ.,  9,  873-82 

( May,  1932);  ibid.,  2nd  ed.,  Mack  Printing  Co.,  Easton,  Pa.,  1934,  pp.  87-98. 

(17)  DEL  Rio,  A.  M.,  "Elementos  de  Orictognosia,"  2nd  ed.,  John  Hurtel,  Phila 

delphia,  1832,  pp.  484-5. 

(18)  BANCROFT,  H.  H.,  "The  Works  of  Hubert  Howe  Bancroft,"  Vol.   12,  A.  L. 

Bancroft  and  Co.,  San  Francisco,  1885,  p.  699. 

(19)  DE   GALVEZ-CANERO,  A.,  "Apuntes   Biograficos   de   D.   Fausto   de  Elhuyar," 

Graficas  reunidas,  Madrid,  1933,  pp.  107-68. 

(20)  BEULLOCH,  "Viage  a  Mexico  en  1828,"  Vol.  2,  El  Album  Mexicano,  Imprenta 

del  Cumplido,  Mexico,  1849,  p.  492;  See  also:  T.  A.  RICKARD,  "Journeys  of 
Observation  among  the  Mines  of  Mexico,"  Dewey  Publishing  Co.,  San 
Francisco,  1907,  pp.  30-1. 

(21)  DEL  Rio,  A.  M.,  "Analysis  of  a  specimen  of  gold  found  to  be  alloyed  with 

rhodium,"  El  Sol,  Dec.  11,  1824;  Am.  J.  Sci.,  11,  298-304  (1826);  Ann. 
chim.  phys.,  [2],  29,  137-47  (1825);  Annals  of  Philosophy,  [2],  10,  251-6 
(Oct.,  1825);  E.  F.  SMITH,  "Chemistry  in  Old  Philadelphia,"  J.  B.  Lippin- 
cott  Co.,  Philadelphia,  1919,  pp.  86-90. 

(22)  DEL  Rio,  A.  M.,  "Nuevo  Sistema  Mineral  de  Sefior  Bercelio  del  Ano  de  1825," 

Imprenta  del  Aguila,  Mexico,  1827,  28  pp. 

(23)  DEL  Rio,  A.  M.,  "Silver  ores  reduced  by  the  method  of  Becquerel,"  Trans.  Am. 

Phil.  Soc.,  N.  ,S.,  4,  60-2  ( 1834).    Read  Nov.  5, 1830. 

(24)  DEL  Rio,  A.  M.,  "On  the  crystals  developed  in  vermiculite  by  heat,"  ibid.,  5, 

137-8  (1837).    Read  Nov.  1,  1833. 

(25)  SHEPARD,  C.  U.,  "Reply  to  'Observations  on  the  treatise  of  mineralogy  of  Mr. 

C.  U.  Shepard/  by  Andres  del  Rio  .  .  .,"  Am.  /.  Sci.,  27,  312-25  (1835); 
A.  M.  DEL  Rio,  ibid.,  30,  384-7  (1836);  ibid.,  31,  131-4  (1837). 

(26)  DEL  Rio,  A.  M.?  "Manual  de  geologia  extractado  de  la  lethaea  geognostica  de 

Bronn  con  los  animales  y  vegetales  perdidos  .  .  .,"  Ignacio  Cumplido, 
Mexico,  1841. 

(27)  DEL  Rio,  A.  M.,  "Suplemento  de  adiciones  y  correcciones  de  mi  Mineralogia 

impresa  en  Filadelfia  en  1832,"  Tipografia  de  R.  Rafael,  Mexico,  1849. 

(28)  MOLES,  E.,  "Discurso  leido  en  el  acto  de  su  recepci6n.    Del  momento  cientifico 

espanol  1775-1825,"  Acad.  ciencias  exactas,  fisicas,  y  naturales  de  Madrid, 
C.  Bermejo,  Madrid,  1934,  pp.  97-105. 

(29)  WITTICH,  E.,  "Zur  Entdeckungsgeschichte  des  Elementes  Vanadium,"  Forsch- 

ungen  und  Fortschritte,  9,  38-9  (Jan.  20,  1933). 


CONTRIBUTIONS  OF  ANDRES  MANUEL  DEL  RIO  405 

(SO)  BARGALLO,  M,  "Homenaje  a  Don  Andres  Manuel  del  Rio  y  Fernandez  en 
ocasion  del  primer  centenario  de  su  muerte  ( 1849-1949 )/*  Ciencia,  10, 
270-8  (1950). 

(31)  OESPER,  RALPH  E5  "Enrique  Moles,"  /   Chem.  Educ ,  13,  368  (Aug.,  1936) 

(32)  DUVEEN,  D   I   and  HERBERT  S   KLICKSTEIN,  "John  Dalton's  'Autobiography/" 

ibid.,  323  333-4  (June,  1955) 

(33)  BARGALXO,   MODESTO,  "La  nuneria  y  la  Metalurgia  en  la  America   espanola 

durante  la  epoca  colonial/'  Fondo  de  Cultura  Economica,  Mexico  and  Buenos 
Aires,  1955,  442  pp. 


Don  Antonio  de  Ulloa,  1716- 
1795.  Spanish  mathematician, 
naval  officer,  and  traveler.  The 
log  of  his  voyage  to  Peru  pub 
lished  in  1748  contains  a  de 
scription  of  platinum. 


A  successful  pursuit  of  science  makes  a  man  the 
benefactor  of  all  mankind  and  of  every  age  (1). 


16 

The  platinum  metals 


The  earliest  scientific  descriptions  of  platinum  are  those  of  Dr. 
Brownrigg  and  Don  Antonio  de  Ulloa  in  the  middle  of  the 
eighteenth  century.  Rhodium,  palladium,  osmium,  and  indium 
were  discovered  in  1803  and  1804}  the  first  two  by  Dr.  Wollaston 
and  the  others  by  his  friend,  Smithson  Tennant.  Thomsons  "His 
tory  of  Chemistry"  and  Berzelius'  correspondence  and  diary 
present  a  pleasing  picture  of  these  two  great  English  chemists. 
Ruthenium,  the  Russian  member  of  the  platinum  family,  was  dis 
covered  much  later  by  Karl  Karlomcli  Klaus,  whose  life  story  was 
beautifully  told  by  Professor  B.  N  Menschutkin  of  the  Poly 
technic  Institute  of  Leningrad. 


PLATINUM 

hen  platinum  was  first  introduced  into  Europe  in  the  eight 
eenth  century,  mineralogists  and  chemists  agreed  that  it  must  be  a 
new  metal  In  1790,  however,  Father  Angelo  Maria  Cortenovis  (1727- 
1801),  an  Italian  antiquarian  of  the  Barnabite  order,  concluded  from  a 
study  of  the  Greek  and  Latin  classics*  that  this  metal  must  have  been 
known  to  the  ancients  and  that  it  must  be  identical  with  the  electrum  of 
the  Greeks  (96).  E,  0.  von  Lippmann  explained,  however,  that  electrum 
was  the  same  as  the  Egyptian  asem,  an  alloy  of  gold  and  silver  (97). 
M.  H.  Klaproth's  analysis  of  "electrum,  a  native  alloy  of  gold  and  silver" 
from  Schlangenberg,  Siberia,  showed  that  this  natural  electrum  contained 
64  parts  of  gold  to  36  of  silver  (98), 

When  M.  Berthelot  analyzed  some  metal  detached  from  a  metallic 
casket  from  Thebes,  he  found  it  to  be  an  alloy  of  platinum  that  was  more 
resistant  to  reagents  than  the  pure  metal.  The  hieroglyphics  on  the 
casket  showed  that  it  had  been  dedicated  to  Queen  Shapenapit,  daughter 
of  King  Psamnetik  I  (seventh  century  B.C.)  (99).  Berthelot  believed 
that  it  had  been  prepared  from  a  native  alluvial  ore  containing  iridium 
and  gold.  Alfred  Lucas,  in  his  "Ancient  Egyptian  Materials  and  In 
dustries,"  referred  to  this  as  the  only  known  occurrence  of  the  intentional 
use  of  platinum  in  ancient  Egypt  (100). 

Although  Pliny  the  Elder's  description  of  a  heavy  white  substance 


408 


DISCOVERY  OF  THE  ELEMENTS 


found  in  the  sands  of  Portugal  and  Galicia  has  been  construed  by  J.  S.  C. 
Schweigger,  F.  A.  Moros,  and  others  as  a  reference  to  platinum,  it  is 
far  more  likely  that  this  was  a  tin  ore  (101,  102, 103).  Neither  Hermann 
Kopp  nor  L.  von  Crell  believed  that  Pliny  could  possibly  have  been 
referring  to  platinum  (41,  104). 

Although  platinum  occurs  as  grains  and  nuggets  in  the  alluvial  sands 
of  many  rivers,  there  is  only  slight  evidence  of  its  use  by  ancient 
peoples.  The  pre-Columbian  Indians,  however,  near  the  place  now  known 
as  La  Tolita,  Esmeraldas,  Ecuador  (39),  produced  white  alloys  of  gold 
and  platinum,  from  which  they  made  many  little  artifacts,  some  of  which 
are  now  preserved  in  the  University  of  Pennsylvania  Museum  in  Phila 
delphia  and  the  Danish  National  Museum  in  Copenhagen.  Since  plati- 


Julius  Caesar  Scaliger,  1484-1558.  Italian 
physician,  scholar,  and  poet.  In  1557  he 
made  a  brief  allusion  to  a  refractory  metal 
which  was  probably  platinum.  His  son 
Joseph  Justus  Scaliger  was  a  famous 
philologist. 


num  cannot  be  melted  with  any  primitive  source  of  heat,  Paul  Bergs0e 
(40)  believes  that  a  little  gold  was  mixed  with  the  grains  of  platinum 
in  order  to  seal  them  together  as  the  gold  was  melted,  and  that  the  sin 
tered  mass  was  then  subjected  to  alternate  heating  and  hammering. 

Less  than  half  a  century  after  Balboa  had  "stood  silent  on  a  peak 
in  Darien,"  facing  the  unknown  ocean,  a  famous  Italian  scholar  and 
poet,  Julius  Caesar  Scaliger,  or  della  Scala,  recorded  the  presence  there 
of  an  unknown  noble  metal.  In  1557  he  made  what  is  probably  the  first 
definite  allusion  to  platinum.  Girolamo  Cardano  (1501-1576),  in  his 
well-known  work  "On  Subtlety,"  had  defined  a  metal  as  "a  substance  which 


THE  PLATINUM  METALS  409 

can  be  melted  and  which  hardens  on  cooling."  In  his  "Exotericarum  exer- 
citationum  liber  quintus  decimus  de  subtilitate  ad  Hieronymum  Carda- 
num,"  Scaliger  pointed  out  that  such  a  definition  would  exclude  mercury 
and  also  another  metal,  found  between  Mexico  and  Darien,  Vhich  no 
fire  nor  any  Spanish  artifice  has  yet  been  able  to  liquefy"  (41,  54). 

Because  of  conflicting  accounts,  it  is  difficult  to  learn  the  truth  about 
Scaliger  s  early  life  (13).  One  of  his  numerous  children,  Joseph  Justus, 
became  a  noted  philologist  (106).  In  an  essay  on  Joseph  Scaliger,  Mark 
Pattison  gave  some  striking  glimpses  of  the  father  (107).  In  another 
eulogy  of  the  great  philologist,  Dominicus  Baudius  said  that  the  elder 
Scaliger  was  "of  greatness  unexampled,  had  he  not  become  the  father 
of  a  son  greater  than  himself  .  .  ."  (JOS). 

Part  of  J.  C.  Scahger's  "Poetics/*  which  had  a  striking  influence  on 
Ben  Jonson,  has  been  translated  into  English  by  F.  M,  Padelford  (118). 
An  autographed  manuscript  of  his  commentaries  on  Aristotle's  "De 
Historia  Animahum"  was  bequeathed  to  the  University  of  Leyden  by 
Joseph  Scaliger,  who  requested  in  his  will  that  the  wax  portrait  of  his 
father  be  "put  in  a  safe  place  where  it  cannot  be  handled  and  damaged 
by  too  much  contact .  .  ."  (108). 

Charles  Wood,  a  metallurgist  and  assayer,  found  in  Jamaica  some 
platinum  from  Cartagena  [Colombia],  and  in  1741  took  some  of  it  to  his 
relative,  Dr.  Brownrigg.  After  preparing  a  thorough  and  accurate 
description  of  the  metal  and  its  properties,  Dr.  Brownrigg  in  1750  pre 
sented  these  specimens  to  the  Royal  Society  of  London.  The  exhibit 
included  the  ore  as  found  in  Nature,  the  purified  metal,  the  fused  metal, 
and  a  sword  with  a  pummel  made  partly  of  platinum  (2). 

Don  Antonio  de  Ulloa,  in  the  log  of  his  famous  voyage  to  South 
America,  which  was  published  in  1748,  gave  a  brief  but  definite  descrip 
tion  of  platmum  (55,  71).  He  was  born  on  January  12,  1716,  at  number 
1  Almirante  Street  in  Seville.  While  still  a  young  child,  he  began  to 
study  mathematics  at  the  Col^gio  Mayor  de  Santo  Tomas.  At  the  age 
of  fourteen  years,  he  entered  service  on  the  galleon  San  Luis,  which  set 
sail  from  Cadiz  under  the  command  of  the  Marques  de  Torre-Blanca. 
After  visiting  the  ports  of  Porto  Bello  and  Havana,  the  storm-tossed  fleet 
ended  its  journey  and  anchored  at  Cadiz  in  September,  17&2  (112). 

At  that  time,  the  Academy  of  Sciences  of  Paris,  greatly  interested 
in  the  shape  and  dimensions  of  the  earth,  was  preparing  to  send  two 
expeditions,  one  to  Lapland  and  the  other  to  Ecuador,  to  measure  degrees 
of  meridian.  In  this  undertaking  Louis  XV  sought  the  aid  of  his  rela 
tive  Philip  V  of  Spain.  Because  of  their  demonstrated  ability,  Don  An 
tonio  de  Ulloa  and  Don  Jorge  Juan  y  Santacilia,  respectively  nineteen  and 
twenty-one  years  of  age,  were  promoted  to  the  rank  of  frigate  lieutenants. 
Setting  sail  on  May  28,  1735,  they  cast  anchor  at  Cartagena  on  July  9th 


410  DISCOVEKY  OF  THE  ELEMENTS 

and  waited  for  the  French  academicians,  After  studying  at  Porto  Bello, 
they  passed  through  the  Chagres  River  of  Panama  to  Cruces.  On  Decem 
ber  29th  they  arrived  at  Panama.  In  Guayaquil,  Ecuador,  Don  An 
tonio  took  advantage  of  an  unavoidable  delay  to  study  the  Guayaquil 
purple  and  the  cacao  plantations.  Proceeding  by  way  of  the  volcanic 
legion  of  Chimborazo,  the  expedition  arrived  at  Quito  on  May  29th. 
After  the  astronomical  measurements  had  finally  been  made,  Don  An 
tonio  embarked  on  the  French  frigate  Notre  Dame  de  la  Deliurance,  which 
was  captured  by  the  British  at  Louisburg,  Cape  Breton.  The  English 
naval  officers  treated  him  with  the  utmost  courtesy  and  kindness,  how 
ever,  preserved  his  scientific  records,  and  guaranteed  him  a  safe  passage 
to  England. 

When  he  petitioned  the  Admiralty  for  the  return  of  his  papers,  says 
Don  Antonio  de  Ulloa,  they  "unanimously,  and  with  pleasure,  granted  the 
contents  of  my  memorial,  nobly  adding  that  they  were  not  at  war  with 
the  arts  and  sciences,  or  their  professors."  Upon  his  arrival  in  London, 
de  Ulloa  was  introduced  to  Martin  Folkes,  the  president  of  the  Royal 
Society,  and  to  many  other  distinguished  men  and  was  elected  to  member 
ship  in  that  society  (32). 

In  1746  de  Ulloa  returned  to  Madrid,  and,  with  Jorge  Juan,  prepared 
for  publication  the  memorable  "Historical  Account  of  the  Voyage  to 
South  America/'  which  was  published  in  1748  (35,  55,  56} .  In  the  preface 
to  his  "Astronomical  and  Physical  Observations,"  Jorge  Juan  said  that 
Ulloa  regarded  platinum  as  a  peculiar  metal  and  anticipated  that  there 
must  be  special  mines  of  it  as  there  are  of  gold  and  silver  ( 55 ) . 

De  Ulloa  described  it  as  follows:  "In  the  district  of  Choco  are  many 
mines  of  Lavadero,  or  wash  gold  .  .  .  several  of  the  mines  have  been 
abandoned  on  account  of  the  platina;  a  substance  of  such  resistance  that, 
when  struck  on  an  anvil  of  steel,  it  is  not  easy  to  be  separated;  nor  is 
it  calcinable;  so  that  the  metal,  inclosed  within  this  obdurate  body, 
could  not  be  extracted  without  infinite  labour  and  charge  .  .  ."  (56,  57). 

De  Ulloa  and  Jorge  Juan  sent  a  dozen  copies  of  this  log  to  members 
of  the  Royal  Society  of  London.  On  December  19,  1748,  William  Watson 
(later  Sir  William)  wrote  as  follows:  "Only  last  Wednesday  I  was  de 
lighted  to  receive  the  copies  of  your  book  which  you  intended  for  me 
and  your  other  friends,  for  which  I  sincerely  thank  you.  .  .  .  On  Thursday 
Mr.  Folkes  did  not  fail  to  present  .  .  .  the  copy  marked  for  the  Royal 
Society.  .  .  .  The  Society  voted  its  special  thanks  to  you  both  for  the 
gift  of  a  book  so  charged  with  curious,  choice,  and  interesting  informa 
tion"  (58). 

Unfortunately,  de  Ulloa's  many  activities  did  not  leave  him  time  for 
a  thorough  investigation  of  the  new  metal,  After  studying  the  sciences 
and  useful  arts  of  several  European  countries,  he  returned  to  Spain  and 


THE  PLATINUM  METALS 


411 


reorganized  the  Schools  of  Medicine  and  Surgery,  established  the  textile 
industry.,  and  developed  the  mercury  mines  of  Almaden.  In  1758  he  was 
sent  to  Peru  to  superintend  the  mercury  mines  of  Huancavelica. 

When  the  Treaty  of  Fontamebleau  gave  Spain  authority  over 
Louisiana,  Charles  III  in  1765  ordered  Don  Antonio  to  take  possession. 
When  he  arrived  at  New  Orleans  in  a  heavy  storm,  the  colonists  gave 
him  "a  respectful,  but  cold  and  somber,  greeting"  (59).  In  his  "History 
of  Louisiana,"  Albert  Phelps  explained:  "He  was  cold,  reserved,  and 
proud,  but  the  source  of  his  dignity— his  reputation  as  a  man  of  learning 
and  science— was  all  unknown  to  Louisiana,  and  therefore  his  assumption 
of  authority,  unsupported  by  any  appearance,  was  taken  to  be  mere 


Sir  William  Watson,  1715-1787.  British 
physician,  naturalist,  and  electrician  who 
contributed  many  original  papers  and 
summaries  of  the  work  of  others  to  the 
Philosophical  Transactions.  In  1750  he 
communicated  Dr.  William  Brownrigg's 
paper  on  platinum  to  the  Royal  Society. 
This  portrait  was  engraved  by  Thorn- 
thwaite  after  a  painting  by  Abbott. 


arrogance  or  pretention"  (60).  Another  historian  stated  that  "his  sci 
entific  spirit,  as  often  happens,  led  him  to  waste  his  time  on  trifling 
details"  (59). 

When  his  fiancee  arrived  from  Peru,  they  were  married  at  the 
Balize  at  the  mouth  of  the  Mississippi  by  the  chaplain  of  the  vessel  which 
had  brought  her.  This  unceremonious  procedure,  together  with  de  Ulloa's 
prolonged  absence  from  New  Orleans,  brought  fresh  criticism  from  the 
colonists,  and  he  was  soon  dismissed  (34),  N.-J  Thiery  de  Menonville, 
a  contemporary  French  botanist  and  traveler,  said,  "I  have  heard  much 
fault  found  with  Don  Uloa  [sic]?  but  all  the  subjects  of  complaint  that 
were  alledged  against  him  were  charges  of  familiarity  unworthy  of  his 
rank,  and  a  shabby  meanness  in  his  domestic  concerns.  He  has  never 


412  DISCOVEKY  OF  THE  ELEMENTS 

given  room  for  anyone  acusing  him  of  injustice  or  cruelty  ...  his  exces 
sive  patience  made  him  to  be  despised  and  dismissed"  (61). 

After  serving  for  a  time  as  commander  of  the  fleet,  de  Ulloa  returned 
to  Spain.  Joseph  Townsend,  a  contemporary  traveler,  gave  the  following 
description  of  his  visit  to  de  Ulloa  at  Cadiz:  "For  my  part,  ...  I  chiefly 
associated  with  Spaniards.  Among  these  the  principal  was  Don  Antonio 
Ulloa,  the  well  known  companion  of  D.  Georg  Juan.  ...  I  found  him 
perfectly  the  philosopher,  sensible  and  well  informed,  lively  in  his 
conversation,  free  and  easy  in  his  manners.  .  .  .  This  great  man, 
diminutive  in  stature,  remarkably  thin  and  bowed  down  with  age,  clad 
like  a  peasant,  and  surrounded  by  his  numerous  family  of  children,  with 
the  youngest,  about  two  years  old,  playing  on  his  knee,  was  sitting  to 
receive  morning  visitors.  .  .  . 

"The  room  was  twenty  feet  long  by  fourteen  wide,  and  less  than 
eight  feet  high.  In  this  I  saw  dispersed  confused,  chairs,  tables,  trunks, 
boxes,  books,  and  papers,  a  bed,  a  press,  umbrellas,  clothes,  carpenters' 
tools,  mathematical  instruments,  a  barometer,  a  clock,  guns,  pictures, 
looking-glasses,  fossils,  minerals,  and  shells,  his  kettle,  basons,  broken 
jugs,  American  antiquities,  money,  and  a  curious  mummy  from  the 
Canary  Islands.  .  .  .  When  I  went  to  take  my  leave  of  him,  on  quitting 
Cadiz,  he  presented  me  with  his  Natural  History  of  South  America,  a 
work  highly  deserving  to  be  translated"  ( 62 ) . 

De  Ulloa  died  on  Le6n  Island  near  Cadiz  on  July  5,  1795.  According 
to  J.  Sempere  y  Guarinos,  he  brought  to  Spain  the  first  knowledge  of 
electricity  and  artificial  magnetism,  and  used  a  solar  reflecting  micro 
scope,  such  as  he  had  seen  in  England,  to  demonstrate  the  circulation 
of  the  blood  in  the  appendages  of  fish  and  various  insects.  From  his 
journeys,  Ulloa  brought  back  a  knowledge  of  the  cinnamon  and  rubber 
trees  and  of  improvements  in  the  arts  of  printing  and  binding.  He  also 
established  the  first  cabinet  of  natural  history  and  the  first  metallurgical 
laboratory  in  Madrid  (58). 

About  two  years  after  the  log  of  de  Ulloa's  voyage  had  been  pub 
lished,  Sir  William  Watson  and  Dr.  William  Brownrigg  contributed  to 
the  Philosophical  Transactions  a  more  detailed  description  of  platinum. 
William  Brownrigg  was  born  at  High  Close  Hall,  Cumberland,  on  March 
24,  1711.  He  studied  medicine  in  London  and  later  in  Leyden  under  H. 
Boerhaave,  B.  S.  Albinus,  and  W.  J.  s'Gravesande,  and  began  to  practise 
inWlutehaven(2,e3,64). 

A  paper  read  by  Watson  before  the  Royal  Society  on  December  13, 
1750,  contained  an  excerpt  from  a  letter,  dated  Whitehaven,  December 
5th  of  the  same  year,  in  which  Dr.  Brownrigg  had  mentioned  some 
experiments  which  a  friend  of  his  had  made  on  "the  semi-metal  called 
Platina  di  Pinto"  (sic!),  a  substance  which  he  had  not  found  mentioned 


THE  PLATINUM  METALS  413 


by  any  writer  on  minerals  (65).  Dr.  Brownrigg  regarded  it  as  strange 
that  such  a  simple  substance  "among  the  metalline  tribe"  should  have 
remained  unknown  to  naturalists.  He  pointed  out  that  the  principle, 
long  accepted  by  assayers,  that  gold  and  silver  may  be  purified  from  all 
other  substances  by  cupellation,  did  not  apply  to  the  new  "semi-metal,"  for 
it,  like  gold,  "resists  the  power  of  fire  and  the  destructive  force  of  lead." 


XXXIII.  I,  I  take  the  freedom  to  inclofe  to  you  an  account  of  a  &**/*/ p 
femi-mecal  called  Platina,  dl  Pinto  *,  which,  fo  far  as  I  know>  hath  notj*ra  <««**- 
been  taken  notice  of  by  any  writer  on  minerals.     Mr  JFfc//,  who  is  Qr& 
of  the  mod  modern,  makes  no  mention  of  it.     Prefuroing  therefore  that 
the  iubject  is  new,  I  requeft  the  favour  of  you  to  lay  this  account  before 
the  jR.  £  to  be  by  them  read  and  publifhed,  if  they  think  it  deftrvirtg  t»  tl*  Royal 
thofc  honours,     I  fhould  fooner  have  published  this-  account,  but  wak- 
ed,  in  hopes  of  finding  leifure  to  make  further  experiments  oo  thif  body  ^  ^  ^  N 
with  fulphureous  and  other  cements ;  aJio  with  Mercury,  and  feveral  496.  p.  584! 
corrofive  msnftrita.    But  thefe  experiments  I  (hall  now  defer,  untUlNov, 
learn  how  the  above  is  received.     The  experiments  which  t  have  related 
were  feveral  of  them  made  by  a  friend,  whofe  exadnets  in  performing 
them,  and  veracity  in  relating  them,  I  can  rely  on :  however,  fbr.grear 
ter  certainty,  I  lhall  myfelf  repeat  them.  Wft. 

U,  D.  F*  x.  5.  tt  Wm,  Watfon,  F  R-  $*  &*tt*  iTOtehw^  Dec.  5 


2.  Although  the  hiftory  of  minerals,  and  other  foflil  ibbftances*  hath  AfW«  */> 
been  diligently  cultivated,  efpeaally  by  the  Moderns}  yet  it  roufc be ^T^K. 
acknowledged,  that,,  among  the  vaft  variety  of  bodies  whic^  arc  *&&'$£!? 
objects  of  that  fcience,  there  ftill  remains  room  for  new  inquiries.   ^  03%  ffa 

No  wonder  that,  among  the  greac,  andaimoft  ihexhaufablevanqfeweft 
of  falts,  ores,  and  other  concretes,  new  appearances,  and  mixttags  be-™"^ 
fore  unknown,  ftiould  daily  be  dtfcovercd  ;  but  diac,  among  bpd|^of 
a  more  fimple  nature,  and  pimcularly  among  the  mctalhne  tribe,,  ** 
ral  diftincl  fpccirs  fhould  mil  remain  almoft  wholly  unknown  to. 
rahfts,  will  doubdefe  appear  more  ftrange  and  cxtraordin^try- 

Gold  is  ufually  efteemed  the  moft  ponderous  of  bodies ;  aw   _    „ 
have  feen,  in  the  pofleffion  of  the  late  ProfdTor  s'Gravefande*  a  metal 
line  fubftice,  brought  from  the  Eaft-ln&t$>  that  was  Specifically  hea- 


Facsimile  Page  from  Volume  X  of  the  Philosophical  Transactions  Abridgment 

showing  William  Watson's  description  of  platumm  and  a  letter  from  Dr.  Brown 
rigg  on  the  same  subject. 

He  added  that  this  "platina"  had  been  presented  to  him  about  nine 
years  before  by  "a  skilful  and  inquisitive  metallurgist  [Mr.  Charles  Wood] 
who  met  with  it  in  Jamaica,  whither  it  had  been  brought  from  Carthagena" 
(Colombia).  Dr.  Brownrigg  believed  it  probable  that  "there  is  great 
plenty  of  this  semimetal  in  the  Spanish  West  Indies,  since  trinkets  made 
of  it  are  there  very  common."  He  mentioned  its  high  melting  point  and 
its  refractoriness  toward  borax  and  other  saline  fluxes.  "But  the  Span- 


414 


DISCOVERY  OF  THE  ELEMENTS 


iards,"  said  he,  "have  a  way  of  melting  it  down,  either  alone  or  by 
means  of  some  flux;  and  cast  it  into  sword-hilts,  buckles,  snuff-boxes,  and 
other  utensils/' 

In  about  1730,  "Don  Jorge  de  Villalonga,  first  viceroy  of  Santa  Fe, 
was  given  a  guard  for  his  rapier  and  some  buckles  of  platina,  but  was 
assured  that  it  had  not  been  sufficiently  joined  or  made  to  coalesce  and 


speter  3ofe$)  Mirers 


it  wn  o«r  'panftr  fruultflr, 
unb 


njif 

wnD  3ufa|en 


von 


nnb 


Rfftntltottt  iJfrofefibr 


unfr  kr  Edpj 


unb 


in 


Title  Page  of  the  German 
Edition  of  Macquer's  Chemi 
cal  Dictionary.  Pierre- Joseph 
Macquer,  1718-1784,  was  one 
of  the  first  chemists  to  investi 
gate  platinum. 


that  it  was  a  brittle  metal,  but  much  heavier  than  the  gold  with  which 
it  was  associated  in  the  mines  of  the  province  of  Citaro  in  the  district 
of  Choco"  (66). 

Sir  William  Watson  said  that  he  had  seen  this  substance  mentioned 
by  no  other  author  except  de  Ulloa.  On  February  13,  1750,  Dr.  Brown- 
rigg  wrote  again  to  Watson,  explaining  that  the  experiments  he  had 
mentioned  in  his  previous  letter  had  been  made  by  Mr.  Charles  Wood, 


THE  PLATINUM  METALS  415 

who  "was  not  ambitious  of  appearing  in  print,"  but  had  permitted  Dr. 
Brownrigg  to  report  his  results  to  the  Royal  Society. 

Dr.  Brownrigg  was  always  extremely  modest  about  his  discoveries, 
and  preferred  to  live  in  comparative  obscurity  in  Cumberland  rather 
than  to  accept  the  wider  opportunities  of  London.  For  his  experiments 
on  choke  damp  and  carbon  dioxide,  Dr.  Brownrigg  was  awarded  the 
Copley  Medal  (113).  In  1772  he  and  Benjamin  Franklin  stilled  with 
oil  the  stormy  Derwent  Lake  (114).  Franklin  once  visited  him  at  the 
paternal  estate  at  Ormathwaite,  where  Dr.  Brownrigg  was  spending  his 
old  age  in  retirement  (115).  He  died  at  Ormathwaite  on  January  6,  1800. 
A  writer  in  Gentleman's  Magazine  said  of  him,  "The  poor  and  the  rich 


Antoine  Baum^  1728-1804.  French 
pharmacist  and  chemist.  Author  of  a 
"Chymie  expenmentale  et  raisonnee"  in 
which  he  discussed  chemical  apparatus, 
chemical  affinity,  fire,  air,  earth,  water, 
sulfur,  gypsum,  alum,  clay,  niter,  gun 
powder,  borax,  arsenic,  glass,  porcelain, 
and  the  common  acids,  alkalies,  metals, 
and  ores  used  in  1773,  His  hydrometer 
scale  is  still  used.  He  was  one  of  the 
first  chemists  to  investigate  platinum 


had  everywhere  somewhat  for  which  they  thanked  him,  and  health  seemed 
only  one  of  the  blessings  which  he  had  to  dispense"  (64). 

Sir  William  Watson  was  a  distinguished  physician,  naturalist,  and 
physicist.  He  was  born  in  London  on  April  3,  1715,  studied  at  the 
Merchant  Taylors'  School,  and  became  apprenticed  to  an  apothecary. 
He  contributed  to  the  Philosophical  Transactions  a  large  number  of 
original  papers  and  many  reviews  of  the  work  of  other  scientists.  His 
long  series  of  brilliant  experimental  researches  on  electricity  brought  him 
great  renown,  For  many  years  he  served  as  physician  to  the  Foundling 
Hospital  in  London.  He  was  knighted  in  1786  and  died  on  May  10th  of 
the  following  year. 


416 


DISCOVERY  OF  THE  ELEMENTS 


The  most  distinguished  chemists  in  Europe  soon  became  intensely 
interested  in  platinum.  Among  those  who  published  papers  on  it  may 
be  mentioned:  H.  T.  Scheffer  (42),  T.  Bergman,  and  J.  J.  Berzelius  in 
Sweden;  William  Lewis  in  England;  A,  S.  Marggraf  in  Germany;  and 
P.-J.  Macquer,  A.  Baume,  Count  G.-L.  Leclerc  de  Buff  on,  L.-B.  Guyton  de 
Morveau,  Rome  Delisle,  A.-L.  Lavoisier,  and  B.  Pelletier  (43)  in  France. 

In  1752  H.  T.  Scheffer  published  a  detailed  scientific  description  of 
platinum,  or  "white  gold/'  as  he  called  it,  and,  with  the  aid  of  arsenic, 
succeeded  in  fusing  it  (42).  Henric  Theophil  Scheffer  was  born  in 
Stockholm  on  December  28,  1710,  where  his  father  was  secretary  to  the 
Royal  Board  of  Mines.  After  serving  an  apprenticeship  under  Georg 
Brandt,  he  established  his  own  laboratory  and  made  trips  to  the  mines 
to  learn  firsthand  the  close  connection  between  smelting  and  assaying. 


Bertrand  Pelletier,  1761-1797.  French 
chemist  and  pharmacist  who  investi 
gated  the  arsenates,  phosphates,  and 
phosphides  of  many  metals,  studied  the 
action  of  phosphorus  on  platinum,  and 
devised  new  methods  for  making  soap 
and  refining  metal  for  clocks.  He 
served  as  inspector  of  the  hospitals  in 
Belgium.  His  son,  Joseph  Pelletier 
(1788-1842),  and  Joseph  Caventou  dis 
covered  quinine,  cmchomne,  strychnine, 
and  brucrne.  See  also  ref.  (89). 


In  his  eulogy,  A.  F.  Cronstedt  told  the  members  of  the  Swedish 
Academy  of  Sciences  how  Scheffer  became  interested  in  platinum:  "In 
his  time,"  said  Cronstedt,  "a  new  metal  happened  to  be  discovered,  which 
had  evidently  not  been  found  in  two  thousand  years,  and  it  was  most 
fitting  that  the  first  investigation  of  such  a  rare  substance  should  fall  to 
this  man  who  was  worthy  of  it, 

"Your  literary  member,  Herr  Rudenskold  [Ulrik  Rudenschold,  1704r- 
1765],  brought  this  honor  to  him  and  to  us;  for  no  sooner  had  Mr.  Watson 
in  London  let  Herr  Bose  [Georg  Matthias  Bose,  1710-1761]  in  Witten 
berg  know  that  something  resembling  a  metal  of  unknown  properties 


THE  PLATINUM  METALS  417 

had  been  brought  over  from  America,  under  the  name  of  Platina  di  Pinto, 
until  Herr  Rudenskold  arranged  to  get  some  of  it  through  his  acquain 
tances  in  Spain. 

"The  little  bit  that  came,"  said  Cronstedt,  'lie  handed  over  to 
Scheffer,  who,  driven  by  his  customary  zeal,  soon  solved  the  mystery  of 
its  nature,  and  showed  in  a  paper  that  it  was  a  peculiar  metal,  different 
from  all  others,  almost  infusible  when  alone,  just  as  noble  as  gold,  and 
less  pliable.  He  anticipated  Mr.  Lewis,  who  made  experiments  on  a 
greater  quantity  of  it  and  later  published  the  results  of  them  in  the 
Transactions  of  the  British  Scientific  Society  [Philosophical  Transactions 
of  the  Royal  Society  (67}],  but  during  the  investigation  neither  was 
aware  of  the  other's  manipulations  and  conclusions,  wherefore  each  of 
them  established  a  special  property  in  addition  to  what  they  in  all  other 
respects  found  to  be  identical. 

"Our  Scheffer,"  said  Cronstedt,  "who  rejoiced  over  this  incontrover 
tible  evidence,  found,  however,  an  error  in  denoting  the  specific  gravity 
of  the  many  alloys  which  Mr.  Lewis  prepared  from  platinum  and  other 
metals,  wherefore  he  corrected  them  in  the  Handlingar  of  this  Society 
in  a  manner  which  bears  witness  that  the  love  of  truth  did  not  turn  the 
head  of  the  person  who  found  it"  (68). 

Scheffer  died  on  August  10,  1759.  As  Cronstedt  said,  'Tie  sought 
diligently  to  follow  the  path  that  leads  to  the  right  goal  after  death,  for 
he  could  not  harbor  the  false  doctrine  that  gold,  which  hinders  and 
leads  astray,  or  panaceas  alleged  to  prolong  life  can  serve  as  remuneration 
for  piety"  (68). 

In  1772  Baron  Carl  von  Sicldngen  made  extended  researches  on 
platinum  and  rendered  it  malleable  by  alloying  it  with  silver  and  gold, 
dissolving  the  alloy  in  aqua  regia,  precipitating  the  platinum  with  am 
monium  chloride,  igniting  the  ammonium  chloroplatinate,  and  hammer 
ing  the  resulting  finely  divided  platinum  to  make  it  cohere  (69).  His 
researches  on  this  subject  were  not  published  until  1782  (70).  Two 
years  later  F.  C.  Achard  prepared  the  first  platinum  crucible  by  fusing 
platinum  with  arsenic  and  volatilizing  off  the  arsenic  (69). 

The  Marques  de  los  Castillejos  presented  the  Basque  Society  of 
Friends  of  their  Country  with  a  large  quantity  of  platinum.  The  Ex- 
tractos  of  this  Society  published  William  Lewis's  dissertation  on  this 
metal  with  the  editorial  note:  "The  Commission  has  made  several  tests 
according  to  this  information  and  has  succeeded  in  applying  the  use  of 
this  metal  to  the  adornment  of  the  handles  of  several  razors  and  knives, 
giving  it  by  admixture  various  tints  of  golden  or  yellow  color"  (66).  After 
a  thorough  investigation  of  this  metal  at  the  Vergara  Seminary,  Pierre- 
Frangois  Chabaneau  (or  Chavaneau)  succeeded  in  making  pure  plati 
num  malleable  ( 66 ) . 


418  DISCOVEKY  OF  THE  ELEMENTS 

Professor  James  Lewis  Howe,  author  of  an  excellent  bibliography 
of  the  metals  of  the  platinum  group,  and  Louis  Quennessen,  head  of  the 
firm  of  Des  Moutis  and  Company,  platinum  refiners,  have  reviewed 
Chabaneau  s  contributions  (71,  72,  73).  Chabaneau  was  bora  at  Non- 
tron,  Dordogne,  in  1754.  An  uncle,  a  monk  of  the  order  of  St.  Anthony, 
encouraged  him  to  study  theology  Although  Chabaneau  was  brilliantly 
successful  in  his  studies,  metaphysical  speculations  were  so  distasteful 
to  him  that  he  antagonized  his  teachers  and  was  expelled  from  the 

school. 

His  penniless  condition  aroused  the  sympathy  of  the  Abbe  La  Rose, 
director  of  a  Jesuit  college  at  Passy,  who  offered  him  the  chair  of 
mathematics.  Although  he  scarcely  knew  arithmetic,  Chabaneau,  then 
only  seventeen  years  old,  was  compelled  by  dire  need  to  accept  this  un 
suitable  position.  Studying  by  firelight  every  night  in  preparation  for 
the  next  day's  teaching,  he  mastered  arithmetic,  algebra,  and  geometry, 
and  soon  became  deeply  interested  in  physics,  natural  history,  and 

chemistry. 

At  the  age  of  twenty  years  he  began  to  give  a  course  of  public  lectures 
Among  his  auditors  were  the  sons  of  the  Count  of  Penaflorida,  who  had 
sent  them  to  France  to  study  and  to  select  professors  for  the  recently 
founded  Vergara  Seminary.     They  finally  induced  Chabaneau  to  go  to 
Vergara  to  teach  French  and  physics. 

Don  Jose"  Celestino  Mutis  mentioned  in  1774  two  portrait  medallions 
of  the  King  made  by  Don  Francisco  Benito,  engraver  at  the  Royal  Mint 
in  Santa  Fe  (Colombia).  One  of  these  was  made  of  an  alloy  containing 
equal  parts  of  copper  and  platinum,  the  other  of  pure  platinum  (74} 
Two  letters  of  Don  Fausto  de  Elhuyar,  long  preserved  with  the  Mutis 
manuscripts  at  the  Botanical  Garden  in  Madrid,  show  that  he  collaborated 
with  Chabaneau  in  the  researches  on  platinum.  Writing  from  Vergara  to 
his  brother  Don  Juan  Jose  in  Bogotd  on  March  17,  1786,  Don  Fausto 
described  their  process  in  detail,  and  estimated  the  value  of  platinum  as 
less  than  that  of  silver.  From  the  other  letter,  written  from  Paris  to  Don 
Juan  Jose  on  May  19th  of  the  same  year,  it  is  evident  that  Chabaneau 
and  tie  two  Elhuyar  brothers  kept  this  process  secret  (75,  76). 

Soon  after  this,  King  Charles  III  created  for  Chabaneau  a  public 
chair  of  mineralogy,  physics,  and  chemistry  at  Madrid,  lodged  him  in 
one  of  the  royal  palaces,  and  provided  him  with  a  valuable  library  and 
a  luxurious  laboratory  (72,  73), 

The  Marques  de  Aranda  had  the  government  turn  over  its  entire 
supply  of  platinum  to  Chabaneau  for  his  difficult  and  puzzling  re 
searches.  When  Chabaneau  removed  the  gold,  mercury,  lead,  copper, 
iron,  etc.,  he  thought  he  had  a  single  metal,  platinum.  As  a  matter  of 
fact,  however,  he  was  still  dealing  with  six  metals,  for  rhodium,  palladium, 


THE  PLATINUM  METALS  419 

osmium,  iridium,  and  ruthenium  had  not  yet  been  discovered.  Small 
wonder  that  he  oftentimes  became  discouraged  by  contradictory  results. 
Sometimes  the  platinum  was  malleable  and  at  other  times  it  was  brittle 
(alloyed  with  iridium),  sometimes  it  was  incombustible  and  non- volatile 
and  at  other  times  (when  an  osmium  alloy  happened  to  be  present)  it 
burned  and  volatilized. 

When  Chabaneau  began  to  work  on  other  subjects,  the  patient 
Marques  de  Aranda  encouraged  him  to  turn  again  to  the  great  research 
on  "white  gold."  Even  when  Chabaneau  finally  lost  his  temper  and 
destroyed  his  apparatus  and  preparations,  the  Marques  still  urged  him 


Jose  Celestino  Mutis,  1732-1808. 
Spanish  botanist,  physician,  and 
ecclesiastic  who  devoted  his  life 
to  studying  the  natural  history  of 
northern  South  America.  He  in 
vestigated  the  cinchona  (or  chin- 
chona )  forests  of  Colombia  ( New 
Granada)  and  collaborated  with 
Don  Juan  Jose  de  Elhuyar  in 
developing  its  mines.  He  stated 
that  the  gold  m  the  ores  of  Choco 
cannot  be  separated  from  the 
platinum  except  by  amalgama 
tion  (87) 


not  to  lose  confidence.  Three  months  later,  the  Marques  found  on  a  table 
in  his  home  a  ten-centimeter  cube  of  metal.  Attempting  to  pick  it  up, 
he  said  to  Chabaneau,  "You  are  joking.  You  have  fastened  it  down  "  The 
little  ingot  weighed  23  kilograms;  it  was  malleable  platinum!  Although 
the  Marques  de  Aranda  had  previously  handled  platinum  only  in  the 
spongy  form,  Chabaneau  had  compressed  a  very  pure  platinum  sponge, 
while  hot,  at  the  moment  of  its  formation,  and  hammered  it,  while  white 
hot,  until  it  cohered. 

The  King,  who  had  often  come  to  the  laboratory  to  watch  the 
progress  of  the  experiments,  had  a  commemorative  medal  struck  in 
platinum,  and  granted  Chabaneau  a  life  pension  on  condition  that  he 


420  DISCOVERY  OF  THE  ELEMENTS 

remain  in  Spain.     The  letters-patent  bearing  the  date  1783  established 
Chabaneau's  priority  in  this  discovery  (72). 

Realizing  that  the  very  infusibility  of  platinum  would  lend  value 
to  objects  made  from  it,  Chabaneau  and  Don  Joaquin  Cabezas  purified 
it,  worked  it,  and  carried  on  a  lucrative  business  in  the  sale  of  platinum 
ingots  and  utensils.  Thus  began  what  Don  Juan  Fages  y  Virgili  has 
called  "the  platinum  age  in  Spain"  (66).  In  1799  Clavijo  Fajardo,  direc 
tor  of  the  Royal  Laboratory  of  Natural  History,  asked  the  Minister  for 
forty  pounds  of  purified  platinum  and  three  arrobas  (1  arroba  =  25 
pounds)  of  the  native  platinum  grains  for  the  use  of  Don  Luis  (Joseph- 
Louis  )  Proust  for  making  crucibles  and  other  utensils,  and  the  government 
granted  even  more  of  it  than  was  requested  ( 66 ) .  Thus  in  a  single  labora 
tory  in  Madrid,  "forty-six  kilograms  of  platinum  in  grains  and  eighteen 
and  one-half  of  the  same  purified  were  brought  in  in  one  day,  that  is  to 
say,  more  platinum  than  we  possess  today  [1909]  in  all  the  official 
laboratories  in  Spain"  (66).  Some  of  the  platinum  extracted  from  the 
gray  sand  which  Don  Antonio  de  Ulloa  had  brought  from  America  was 
made  into  a  magnificent  communion  cup  for  the  chapel  of  the  Royal 
Palace  in  Madiid  (77).  In  other  parts  of  the  world,  too,  platinum  was 
then  relatively  abundant.  In  1808  Fredrick  Accum  sold  some  platinum 
to  Piofessor  William  Peck  of  Harvard  University  for  about  7  cents  a 
gram  ("Va  oz  pure  platina  in  slips  4  shillings")  (90). 

Late  in  life  Chabaneau  renounced  his  pension  in  order  to  seek  rest 
and  restoration  of  his  health  near  his  native  village.  He  died  in  1842 
at  the  age  of  eighty-eight  years.  Jules  Delanoue,  a  contemporary,  de 
scribed  him  as  "a  fine-looking  old  man,  with  pleasing  and  regular  fea 
tures,  bearing  much  resemblance  to  those  of  our  good  and  lamented 
Beranger.  His  conversation  was  charming  and  always  instructive. 
Friend  and  contemporary  of  Volney,  of  Cabanis,  of  Lavoisier,  he  was  nour 
ished  upon  their  ideas  and  imbued  with  their  spirit,  and  they  were  pleas 
ingly  reflected  in  his  conversation"  (72,  73). 

When  Chabaneau  took  some  of  his  ingots  to  Paris,  M.  Jeanety  made 
from  them  some  beautiful  pieces  of  jewelry  and  became  so  interested  that 
he  gave  up  his  craftmanship  in  gold  and  silver  to  devote  all  his  time  to 
the  working  of  platinum  (78).  In  the  Jeanety  process,  objects  were 
fashioned  from  a  platinum-arsenic  alloy  and  heated  to  expel  the  arsenic 
(91).  Guyton  de  Morveau,  Sir  Joseph  Banks,  and  some  of  the  scientists 
in  Sweden  and  the  Netherlands  ordered  from  him  their  platinum  crucibles 
and  ingots.  Jeanety  also  made  platinum  snuffboxes,  watchchains,  spoons, 
toothpick  boxes,  blowpipes,  and  a  set  of  buttons  (78,  79).  The  prices 
were  lower  than  for  the  corresponding  articles  in  gold 

In  reporting  Jeanety 's  process  to  the  French  Bureau  of  Consultation 
in  1792,  C.-L.  Berthollet  and  Bertrand  Pelletier  stated  that  the  gold 


1HE  PLATINUM  METALS  421 

from  the  Novita  and  Citaria  mines  north  of  Choco  was  separated  from 
the  platinum  by  sorting  or  by  amalgamation.  Since  platinum  could  be 
used  to  alloy  and  adulterate  gold,  and  since  such  alloys  resisted  parting, 
the  Spanish  government  ordered  that  the  platinum  be  thrown  into  the 
rivers.  "The  Choco  gold,"  said  Berthollet  and  Pelletier,  "is  then  sent  to  be 
coined  in  the  two  mints  at  Santa  Fe,  to  those  in  Bogota  and  Popayan, 
where  any  platinum  which  may  have  remained  with  the  gold  is  again 
sorted  out.  Royal  officers  guard  it,  and  when  there  is  a  certain  quantity 
of  it,  they  come  with  witnesses  to  throw  it  into  the  Bogota  River  two 
leagues  from  Santa  Fe  and  into  the  Cauca  River  one  league  from  Popayan. 
The  platinum  always  occurs  in  little  grains,  some  of  them,  however,  are 
quite  large;  there  is  even  one  in  the  cabinet  of  the  Vergara  Academy  of 
the  size  of  a  pigeon's  egg"  ( 78 ) . 

An  article  on  the  platinum  mines  of  Colombia  published  in  volume 
6  of  the  Medical  Repository  states  that  "Three  hundred  pounds  of  platina 
were  imported  into  New  York  in  October,  1802,  from  the  Island  of 
Jamaica.  But  it  was  not  a  native  production  of  that  place.  It  was  brought 
from  the  continental  dominions  of  Spain.  As  the  exportation  of  platina 
is  prohibited  by  the  government,  this  quantity  was  smuggled  off  in 
small  parcels.  In  the  course  of  certain  secret  mercantile  transactions, 
these  different  collections  found  their  way  from  the  Spaniards  to  a 
British  subject,  who  brought  to  this  market  the  above-mentioned  quantity, 
which  is  but  a  part  of  what  he  had  gathered  together.  Such  a  quantity 
of  the  rarest  of  the  metals,  and  of  one  which  is  believed  to  be  peculiar 
to  America,  and  known  to  Europe  only  about  the  middle  of  the  eight 
eenth  century,  afforded  an  excellent  opportunity  of  examining  its  condi 
tion  when  offered  for  sale  as  an  article  of  commerce"  (116). 

Dr.  Samuel  Latham  Mitchill,  editor  of  the  Medical  Repository, 
carefully  examined  and  described  this  metal  and  added  that  "Baron 
Carendeffez  has  subjected  parcels  of  this  platina  to  a  great  many  experi 
ments,  which  he  intends  to  publish  at  large.  .  .  .  The  mines  in  the  Island 
of  Chaco  [Choco,  Colombia]  afforded  it:  These  are  in  Terra  Firma, 
about  three  hundred  miles  up  the  River  Magdalena,  and  south-west  some 
distance  from  Santa  Fe,  and  are  reckoned  among  the  most  pure  and  pro 
ductive  in  America.  The  platina  is  found  among  the  gold,  and  the  grains 
of  the  two  metals  are  washed  from  the  sands  together,  and  afterwards 
separated.  All  the  platina,  as  well  as  all  the  gold,  is  deposited  in  the 
adjoining  custom-house,  and  kept  by  the  king's  officers.  It  is  not  cer 
tainly  known  what  becomes  of  the  platina.  For  though  it  is  reported 
that  the  policy  of  the  government  directs  it  to  be  thrown  away,  and  com 
mitted  to  the  currents  of  deep  rivers,  yet  there  is  a  belief  that  the  whole 
quantity  collected  is  transported  to  Spain.  All  commerce  in  platina  is 
forbidden  under  penalty  of  death:  consequently  none  can  be  procured  but 


422  DISCOVERY  OF  THE  ELEMENTS 

by  smuggling,  and  at  very  great  risk.  The  first  cost,  fees  to  assistants, 
and  extraordinary  hazards  in  this  contraband  trade  amounted  to  so 
much  that  the  owner  of  this  parcel  said  it  stood  him  in  forty  dollars  a 

pound"  (116), 

In  1818  French  and  English  journals  contained  a  description  of  an 
enormous  platinum  nugget  weighing  1  pound,  9  ounces,  and  1  dram, 
which  had  been  found  by  Justo,  a  Negro  slave  of  Don  Ignacio  Hurtado, 
proprietor  of  the  Condoto  gold  mine  at  Novitd,  Choco.  It  was  sent 
with  the  Mutis  collections  to  the  King  of  Spain,  who  deposited  it  in  the 
Royal  Museum  at  Madrid  (117). 

William  Lewis  believed  that  platinum  may  have  been  the  sub 
stance  used  by  alchemists  for  "augmenting"  gold.  "These  properties," 
said  he,  "together  with  the  place  where  it  is  found,  and  the  prohibition 
said  to  be  laid  upon  its  exportation  by  the  King  of  Spain,  afford  sufficient 
grounds  to  presume  that  the  Smiris  Hispanica  of  the  alchemists,  em 
ployed  for  augmenting  gold,  was  no  other  than  this  Platina  or  some 
mineral  containing  it;  more  especially  as  Becher  expressly  declares  that 
this  augmentation  was  really  an  abuse;  that  the  Gold  so  augmented  was 
pale  and  brittle;  and  that  though  it  stood  all  the  established  tests  of 
perfect  Gold,  yet  it  would  not  bear  amalgamation  with  Quicksilver,  the 
Mercury  retaining  the  Gold  and  throwing  out  the  Smiris  in  form  of 
a  reddish  powder.  Platina  mixed  with  Gold  is  thrown  out  in  the  same 
manner;  though  it  is  not  easy  by  this  method  to  obtain  a  perfect 
separation"  ( 105 ) . 

Alexander  von  Humboldt  stated  in  1826  that  platinum  "has  not 
yet  been  discovered  north  of  the  isthmus  of  Panama  on  the  North  Ameri 
can  continent.  Platina  in  grains  is  found  only  in  two  places  in  the  known 
world,  that  is  to  say,  in  Choco,  a  province  in  the  kingdom  of  New 
Granada,  and  near  the  coasts  of  the  Southern  Sea  in  the  province  of 
Barbacoas  between  the  second  and  sixth  degrees  of  north  latitude.  .  .  . 
The  placers  which  at  present  yield  platina  are  located  south  of  the 
threshold  (umbral)  which  separates  the  headwaters  of  the  Rio  Atrato 
from  those  of  the  Rio  San  Juan.  ...  It  is  absolutely  false  that  platinum 
has  ever  been  found  near  Cartagena,  at  Santa  Fe  de  Bogoti,  on  islands 
of  Puerto  Rico  or  the  Barbadoes,  or  in  Peru,  even  though  these  localities 
have  been  mentioned  in  excellent  and  well-known  works  .  .  /*  (109). 

Humboldt  obtained  much  of  this  information  from  Don  Joaquin 
Acosta,  a  well-informed  young  army  officer  of  the  Republic  of  Colombia. 
In  July,  1826,  just  as  his  "Political  Essay  on  New  Spain"  was  ready  for 
the  press,  Humboldt  learned  that  J.-B.  Boussingault  had  found  round 
grains  of  platinum  in  the  gold-bearing  pacos  (reddish  silver  ores)  of 
the  veins  of  Santa  Rosa  and  the  Osos,  ten  leagues  northwest  of  Medellin 
(109). 


THE  PLATINUM  METALS  423 

A.  D.  Lumb  stated  in  1920  in  his  monograph  on  the  platinum  metals 
that  Colombia  is  the  second  largest  producer  of  platinum  in  the  world; 
that  the  principal  source  of  supply  is  at  the  head  of  the  San  Juan  River, 
which  enters  the  Pacific  Ocean  north  of  Buenaventura,  the  richest  de 
posits  occurring  in  the  tributaries  of  the  San  Juan;  that  platinum  is  also 
obtained  from  the  Upper  Atrato  River,  which  flows  northward  to  the 
Caribbean  Sea  (Gulf  of  Darien),  and  that  the  area  including  the  water 
sheds  of  the  San  Juan  and  Upper  Atrato  Rivers  is  known  as  the  Choco 
district  (110). 

Although  the  discovery  of  platinum  in  Choco  is  usually  attributed 
to  the  eighteenth-century  explorer  Don  Antonio  de  Ulloa,  J.-B.  Boussin- 
gault  believed  that  the  first  Spanish  gold-seekers  of  the  sixteenth  cen 
tury  could  not  have  failed  to  observe  the  peculiar  "white  gold"  which 
settled  out  with  the  true  gold  in  the  panning  process  (111).  Don  Jose 
Celestmo  Mutis  of  Bogota  also  stated  that  platinum  was  known  in  New 
Granada  even  before  de  Ulloa  described  it  (74). 

When  J.-B,  Boussingault  had  charge  of  the  metallic  mines  of  Colom 
bia,  the  Congress  of  that  country  voted  that  a  platinum  equestrian  statue 
of  Simon  Bolivar  be  erected  in  Bogota.  Charged  with  the  duty  of 
executing  this  order,  Boussingault  drew  up  a  report  showing  that  the 
production  of  all  the  mines  in  the  country  would  be  insufficient  for  this 
purpose  and  that  it  would  be  impossible  to  cast  a  statue  from  this  re 
fractory  metal.  On  the  advice  of  a  superior  official,  he  withheld  the  re 
port,  however,  and,  to  shield  the  lawmakers  from  embarrassment,  merely 
agreed  to  carry  out  the  commission  to  the  best  of  his  ability.  When  the 
Congress  had  had  time  to  forget  about  the  statue  of  Bolivar,  the  two 
kilograms  of  platinum  which  had  been  carefully  saved  were  made  into 
the  apparatus  for  the  laboratory  of  chemical  engineering  (80). 

In  1774  Joseph  Priestley  wrote:  "Nothing  would  be  easier  than  to  aug 
ment  the  force  of  fire  to  a  prodigious  degree  by  blowing  it  with  dephlogis- 
ticated  air  [oxygen]  instead  of  common  air. ...  Possibly  platina  might  be 
melted  by  means  of  it"  ( 95 ) .  In  1801  Robert  Hare,  then  only  twenty  years 
old,  described  before  the  Chemical  Society  of  Philadelphia  his  oxyhydro- 
gen  blowpipe,  with  which  he  could  fuse  platinum.  Two  years  later 
he  reported  to  the  American  Philosophical  Society  that  he  had  succeeded 
in  volatilizing  this  metal  (81).  Hare's  student,  Joachim  Bishop,  later 
founded  the  American  platinum  refining  industry  (82).  It  was  not  until 
after  the  experiments  of  Wollaston,  however,  that  the  working  of  plati 
num  became  easy  (3). 

William  Hyde  Wollaston,  the  son  of  an  Episcopal  clergyman,  was 
born  as  East  Dereham,  Norfolkshire,  England,  on  August  6,  1766.  His 
childhood  was  not  a  lonely  one,  for  he  had  fourteen  active  brothers  and 
sisters.  After  studying  at  Cambridge,  he  received  his  medical  degree  at 


424 


DISCOVERY  OF  THE  ELEMENTS 


Courtesy  Edgar  Fahs  Smith  Memorial  Collection 


Robert  Hare,  1781-1858,  Professor  of  chemistry  at  the  University  of  Penn 
sylvania.  At  the  age  of  twenty  years  he  invented  the  oxy-hydrogen,  or  com 
pound,  blowpipe,  with  which  he  fused  and  volatilized  platinum  and  other 
refractory  substances.  He  was  most  ingenious  in  devising  chemical  apparatus. 


the  age  o£  twenty-seven  years.    Although  he  practiced  his  profession  for 

a  time  at  Bury  St  Edmunds,*  he  retired  in  1800  and  went  to  live  in 

London,  in  order  that  he  might  devote  all  his  time  to  physical  science 

(4,88). 

*  John  Winthrop  the  Younger  once  attended  grammar  school  at  this  place. 


THE  PLATINUM  METALS  425 

For  half  a  century  after  its  discovery  platinum  had  few  uses  because 
of  the  difficulty  of  working  it.  Dr.  Wollaston  found,  however,  that 
spongy  platinum  becomes  malleable  when  strongly  compressed  and  that 
it  can  be  annealed  and  hammered.  This  process  made  possible  the  wide 
spread  use  of  the  metal  for  laboratory  apparatus,  and  the  income  from  it 
enabled  Wollaston  to  retire  from  his  medical  practice  at  the  early  age 
of  thirty-four  years  and  devote  the  rest  of  his  life  to  scientific  research. 
He  specified  the  exact  composition  of  the  aqua  regia  which  would  dis 
solve  the  platinum  without  dissolving  the  iridium,  and  the  proper  method 
of  expelling  the  ammonium  chloride  without  making  the  fine  particles 
of  platinum  cohere.  The  pulverizing  was  done  with  the  hands  and  with 
a  wooden  mortar  and  pestle,  for  harder  surfaces  burnished  the  platinum 
so  that  it  could  not  be  welded.  The  powder  was  then  thoroughly  washed 
with  water,  and,  while  still  wet,  strongly  compressed  in  a  mould,  heated 
in  a  wind  furnace,  and  struck,  while  hot,  with  a  heavy  hammer. 

On  April  22,  1813,  Berzelius  wrote  from  Stockholm  to  Dr.  Alexandre 
Marcet  of  London: 

When  you  see  Dr.  Wollaston  give  him  a  thousand  compliments  from  me 
and  then  ask  him  if  it  would  he  possible  to  have  a  little  malleable  platinum,  not 
separated  from  its  natural  alloy  with  palladium,  rhodium,  etc  ,  to  make  a  cru 
cible.  The  crucibles  I  have  bought  recently  from  Gary  are  of  a  metal  noticeably 
purer  than  those  which  I  formerly  had,  and  for  that  very  reason  infinitely  more 
susceptible  to  attack  by  other  substances  (5). 

About  two  weeks  later  Dr.  Marcet  replied: 

Wollaston  laughs  at  the  idea  that  you  want  him  to  get  you  some  impure 
platinum  He  asks  me  to  suggest  that  you  alloy  pure  platinum  with  a  little 
silver,  as  the  surest  means  of  increasing  its  durability  (6>). 

On  February  24,  1829,  Berzelius  wrote  to  Eilhard  Mitscherlich, 
"Wollaston's  death  grieves  me.  His  specifications  for  making  platina 
pliable  were  circulated  at  the  same  time  as  the  news  of  his  death.  As 
I  got  indium  to  cohere  in  an  analogous  manner,  I  was  struck  all  the  more 
by  his  simple  method,  went  out  into  the  laboratory,  where  I  had  a 
wet  filter  with  platina  on  it,  partly  washed,  which  I  pressed  in  a  vice, 
dried,  and  ignited  over  a  spirit  lamp  in  a  small  platina  crucible,  and  got 
it  so  coherent  that  it  could  no  longer  be  broken  with  the  fingers  and 
could  easily  be  cold-hammered.  That's  as  far  as  I  have  yet  gone.  That 
was  ten  minutes'  work,  then  I  had  to  let  it  wait  for  a  better  time"  (S3). 

That  Berzelius  made  good  use  of  Wollaston's  process  is  evident  from 
his  letter  to  F.  Wohler  written  on  May  1,  1829: 

We  are  now  re-casting  all  our  old  soldered  platinum  crucibles  by  Wollas 
ton's  method  of  making  platinum  pliable;  it  goes  like  a  dance.  I  think  Wollaston 


426 


DISCOVERY  OF  THE  ELEMENTS 


must  have  laughed  inside  over  the  many  elaborate  methods  which  have  been 
used  in  vain  for  this  purpose,  when  his  is  so  simple.  It  seems  that  by  heating 
the  bottom  of  the  crucible  glowing  hot  in  Sefstrom's  forge,  the  formation  of 
bubbles  can  be  entirely  prevented  (7) . 

In  preparing  solid  platinum  from  its  powder,  Wollaston  foreshadowed 
modern  methods  of  powder  metallurgy,  by  which  the  powders  of  refrac 
tory  metals,  such  as  tungsten,  molybdenum,  tantalum,  and  columbmm, 
can  be  fabricated  into  useful  articles  (849  86). 


N.  G.  Sefstrom's  Portable  Eight-Blast 
Forge.  Fig.  20  Vertical  section.  Fig. 
21.  Transverse  section  a  ...  a  are  the 
eight  conical  tuyeres  from  die  bellows. 
With  small  pieces  of  dust-free  wood  char 
coal  as  fuel,  Sefstrom  melted  platinum  in 
this  forge. 


From  Berzehus*  "Lehrbuch  der  Chenue' 


The  technical  working  of  massive  platinum  should  be  ascribed,  how 
ever,  to  Thomas  Cock,  a  brother-in-law  of  the  platinum-refiner  P.  N. 
Johnson,  rather  than  to  Wollaston.  Cock  worked  out  the  process  in 
William  Allen's  laboratory  at  Plough  Court  and,  at  Allen's  request,  com 
municated  it  to  Wollaston  (51).  According  to  G.  Matthey,  P.  N.  John 
son  was  the  first  to  manufacture  platinum  on  a  commercial  scale  and 
the  first  to  prepare  a  large  and  perfect  sheet  of  the  pure  metal.  James 
Lewis  Howe  has  stated  that  Chabaneau's  process  was  rediscovered  by 
Knight  and  possibly  also  by  Cock  (72). 

Apollos   Apollosovich   Musin-Pushkin    (1760-1805)    of   St.    Peters- 


THE  PLATINUM  METALS 


427 


^^^ 


Edgar  Fahs  Smith  Memorial  Collection, 
University  of  Pennsylvania 

A  Page  from  Sefstrom's  Laboratory  Notes.*  Translation:  Cinchona  reactions. 
5  Ibs.  cortex  Peruvian,  first  quality,  with  the  sea  captain  Rip  a  from  Amsterdam, 
belongs  to  Mazer  and  Co.  Board  of  Health,  minutes  for  Sept.  16,  1816.  Bark 
very  fine  dark  gray.  Infusion  clear,  quite  weak  quinine  taste,  gave  with  iron  solu 
tion  a  dark  green  precipitate.  Antimony  tartrate,  very  weak  opalescence.  Infusion 
of  nutgalls,  very  heavy  white  precipitate  like  that  of  gelatin  and  nutgalls,  Gelatin 
solution,  faint  opalescence.  It  is  no  good.  Stockholm,  Sept.  22,  1816.  N.  G, 

Sefstrom,  M.D.,  Adjunct  in  Chemistry. 

*  The  writer  is  deeply  grateful  to  Miss  Mary  Larson  of  the  Zoology  Department  at  the 
University  of  Kansas  and  to  Mr,  Einar  Bourrnan  for  the  translation  of  this  letter  from 
the  Swedish  and  for  assistance  in  securing  Swedish  translations. 


428  DISCOVERY  OF  THE  ELEMENTS 

burg  investigated  platinum  between  the  years  1797  and  1805,  He  pre 
pared  platinum  amalgam  by  triturating  mercury  with  ammonium  chloro- 
platinate  or  by  triturating  platinum  sponge  powder  with  a  fivefold 
amount  of  mercury  (91).  He  then  produced  malleable  platinum  by 
placing  this  amalgam  in  a  wooden  mold,  heating  the  mold  to  volatilize 
the  mercury,  and  keeping  the  platinum  metal  white  hot  for  two  hours 
or  more.  The  wooden  molds  were  burned. 

In  his  lectures  in  1817,  W.  T.  Brande  stated  that  platinum  "may  be 
considered  as  the  exclusive  product  of  South  America"  (46).  In  1819, 
however,  a  white  metal  was  observed  in  the  gold  placers  on  the  eastern, 
or  Siberian,  slopes  of  the  Urals,  south  of  Ekaterinburg  (Sverdlovsk) 
(69).  In  1822  I.  I.  Varvinskii,  director  of  the  Gold-smelting  Laboratory 
of  Ekaterinburg,  showed  that  it  contained  platinum,  and  V.  V,  Liubarskii, 
an  assayer  of  St.  Petersburg,  later  proved  it  to  be  osmiridium.  In  1824 
platinum  was  discovered  north  of  Ekaterinburg  in  the  Urals  (36). 

In  1826,  thus  two  years  before  Wollaston  disclosed  his  secret  process, 
P.  G.  Sobolevskii  and  V.  V,  Liubarskii  of  St.  Petersburg  devised  a  cheap 
method  of  preparing  malleable  platinum  from  the  spongy  metal  resulting 
from  the  calcination  of  ammonium  chloroplatinate.  Early  in  the  follow 
ing  year  they  demonstrated  their  method  publicly  before  the  Mining 
Cadet  Corps  and  the  Scientific  Committee  on  Mining  and  Salt  Industries. 
For  this  invention  they  received  gifts  from  Emperor  Nicholas  L  Their 
method  was  essentially  the  same  as  WoUaston's  secret  process  (91). 

When  Alexander  von  Humboldt,  Gustav  Rose,  and  Christian  Gott 
fried  Ehrenberg  made  a  scientific  expedition  to  Russia  in  1829  the 
Russian  Minister  of  Finance  E.  F,  Kankrin  made  arrangements  for 
their  comfort  and  security.  Humboldt  made  important  observations  on 
the  gold-  and  platinum-bearing  alluvial  deposits  of  the  Urals  (92). 
Professor  B.  N.  Menschutkin  published  in  the  Journal  of  Chemical  Educa 
tion  an  excellent  historical  sketch  of  the  Russian  platinum  (36). 

In  1828  the  Russian  government  authorized  the  coinage  o£  large 
amounts  of  Siberian  platinum  acquired  from  Count  Demidoff  (85).  The 
following  notice  appeared  in  Philosophical  Magazine  in  December  of 
that  year:  "A  letter  from  Professor  Breithaupt  to  Dr.  Schweigger-Seidel, 
an  extract  from  which  is  given  in  a  late  Number  of  the  Jahrbuch  der 
Chemie  &c.,  confirms  the  statement,  some  time  since  made  by  the  news 
papers,  that  the  Russian  Government  had  resolved  to  coin  a  large  sum 
in  Siberian  platina.  It  appears  that  Count  Demidoff,  the  proprietor  of 
the  locality  where  the  platina  was  discovered,  has  disposed  of  to  the 
Government  the  quantity  of  that  metal  which  had  been  collected.  He 
has  sent  four  young  Russians,  destined  for  official  situations  in  Siberia, 
to  be  educated  at  the  Mining  Academy  of  Freyberg"  (85). 

Between  the  years  1828  and  1845  a  total  of  14,600  kilograms  of 


THE  PLATINUM  METALS 


429 


platinum  was  coined  in  three-,  six-,  and  twelve-ruble  denominations  (36). 
In  1846  the  platinum  coins  were  withdrawn  from  circulation. 

PALLADIUM 

As  early  as  1700,  or  more  than  a  century  before  palladium  was  dis 
covered,  Brazilian  miners  became  familiar  with  a  natural  alloy  which 
they  called  prata  (silver),  ouro  podre  (worthless,  or  spoiled  gold),  or 
ouro  branco  (white  gold)  (44).  In  about  1780  a  silver-white  gold  bar 
at  the  Sahara  smelting-house  broke  into  several  pieces  under  the  impact 
of  the  die.  This  gold  had  come  from  St.  Anna  dos  Ferros,  near  Itabira 
do  Dentro,  Minas  (44).  In  1798  Jose  Vieira  do  Couto  mentioned  several 
localities  in  Brazil  where  a  silver- white  "platinum"  was  to  be  found.  This 
was  probably  the  alloy  palladium-gold. 


From  Eerzelius1  "Lehrbuch  der  Chemie" 
Bellows  Used  with  Sef Strom's  Forge 


In  1803  Dr.  Wollaston  succeeded  in  separating  two  new  metals 
from  platinum.  He  dissolved  the  crude  metal  in  aqua  regia,  evaporated 
off  the  excess  acid,  and  added  a  solution  of  mercuric  cyanide.,  drop  by 
drop,  until  a  yellow  precipitate  appeared.  When  this  substance  was 
washed  and  ignited,  a  white  metal  remained.  By  heating  the  yellow 
precipitate  with  sulfur  and  borax  he  also  succeeded  in  obtaining  a 
button  of  the  new  metal,  which  he  named  palladium  in  honor  of  the 
recently  discovered  asteroid,  Pallas  (6). 


430  DISCOVERY  OF  THE  ELEMENTS 

The  first  knowledge  that  the  London  public  received  of  this  dis 
covery  was  an  anonymous  handbill  offering  the  metal  for  sale.  The 
humorous  and  pathetic  story  of  the  young  Irish  chemist,  Richard  Chenevix 
(8),  who  believed  the  new  metal  to  be  fraudulent  and  who  tried  to 
prove  that  it  was  a  platinum  amalgam,  has  been  told  in  the  Journal  of 
Chemical  Education  by  White  and  Friedman  (21 )  and  by  Desmond  Reilly 
(130). 

After  considerable  polemics,  Chenevix'  claim  that  the  palladium  was 
merely  an  amalgam  of  platinum  was  disproved,  and  Dr.  Wollaston  wrote 
in  1804:  "Notwithstanding  I  was  aware  that  M.  Descotils  had  ascribed 
the  red  colour  of  certain  precipitates  and  salts  of  platina  to  the  presence 
of  a  new  metal;  and  although  Mr.  Tennant  had  obligingly  communicated 
to  me  his  discovery  of  the  same  substance,  as  well  as  of  a  second  new 
metal,  in  the  shining  powder  that  remains  undissolved  from  the  ore 
of  platina;  yet  I  was  led  to  suppose  that  the  more  soluble  parts  of  this 
mineral  might  be  deserving  of  further  examination,  as  the  fluid  which 
remains  after  the  precipitation  of  platina  by  sal  ammoniac  presents  ap 
pearances  which  I  could  not  ascribe  to  either  of  those  bodies  or  to  any 
other  known  substance"  (120).  Dr,  Wollaston  added  that  "the  metallic 
substance  which  was  last  year  offered  for  sale  by  the  name  of  Palladium 
is  contained  (though  in  very  small  proportion)  in  the  ore  of  platina" 

(130). 

N.-L.  Vauqueh'n  paid  eloquent  tribute  to  the  excellence  of  these 
researches:  "Though  Dr.  Wollaston  operated  on  only  one  thousand  grains 
of  the  ore  of  platinum,  and  had  at  the  most  only  six  or  seven  grains  of  each 
of  the  new  metals  at  his  disposal,  yet  he  recognized  their  principal 
properties,  which  does  infinite  honour  to  his  sagacity;  for  the  thing 
appears  at  first  view  incredible.  For  my  part,  though  I  employed  sixty 
marcs  [15  kilograms]  of  platinum  ore,  I  found  it  very  difficult  to  sepa 
rate  exactly  the  palladium  and  rhodium  from  the  platinum  and  the  other 
metals  which  exist  in  that  ore,  and  especially  to  obtain  them  perfectly 
pure"  (45). 

At  Dr.  Wollaston's  suggestion  palladium  was  alloyed  with  gold  and 
used  "for  the  graduated  part  of  the  great  astronomical  circle  erected  at 
the  Royal  Observatoiy  by  Mr.  Troughton"  (46).  Dr.  Wollaston  em 
phasized  the  desirability  of  using  palladium  weights  for  precise  work. 
A  set  of  tli em  which  once  belonged  to  Thomas  Thomson  has  been  de 
scribed  in  the  Journal  of  Chemical  Education  (47). 

In  1809-10  Joseph  Cloud,  chemical  director  of  the  Philadelphia 
Mint,  discovered  an  alloy  of  gold  and  palladium  in  two  ingots  of  gold 
from  Brazil  (48,  49).  The  following  account  of  this  discovery  is  to  be 
found  in  Nicholsons  Journal  for  1812:  "In  1807  about  820  ounces  of 
gold  bullion  were  brought  into  the  mint  of  the  United  States.  They 


THE  PLATINUM  METALS  431 

consisted  of  120  small  ingots,  each  stamped  on  one  side  with  the  arms  of 
Portugal  and  the  inscription  Rio  das  Montis,  and  on  the  other  with  a 
globe.  The  fineness  of  each  ingot  too  was  marked  on  it.  Among  these 
were  two  differing  from  the  others  so  much  in  colour  that  Mr.  Cloud 
preserved  one,  weighing  3  oz.  11  dwts.,  12  grs.,  to  examine  it  .  .  ."  (49}. 

Eugen  Hussak  stated  that  the  inscription  on  these  ingots  was  not  "Rio 
das  montis,"  but  Rio  dos  Mortes,"  which  is  near  S.  Joao  del  Rey  (44). 
Although  native  gold  usually  contains  some  silver,  copper,  or  other  metals, 
Cloud  found  this  ingot  to  be  alloyed  only  with  palladium  ( 49 ) .  Although 
this  alloy  contained  no  easily  oxidizable  metal,  silver,  nor  platinum,  Cloud 
obtained  from  it  a  button  of  palladium.  Since  palladium  had  previously 
been  obtained  only  from  impure  platinum,  some  chemists  may  still  have 
believed  with  Richard  Chenevix  that  it  must  be  an  alloy  of  platinum. 
Cloud's  isolation  from  the  platinum-free  ingots  of  a  metal  which  proved 
to  be  identical  with  Dr.  Wollaston's  palladium  afforded  strong  evidence 
that  the  latter  must  be  an  individual  metal  and  not  an  alloy  of  plati 
num  (50). 

Although  neither  Couto  nor  Cloud  had  been  certain  whether  the 
palladium-gold  was  a  natural  alloy  or  an  artificial  alloy  of  native  palladium 
with  native  gold,  Berzelius  in  1835  analyzed  some  of  the  natural  "ouro 
podre"  which  the  geologist  E.  Pohl  of  Vienna  had  sent  him  from  Capitania 
Porpez  or  [Goyaz],  Brazil,  and  found  it  to  consist  of  about  86  per  cent 
of  gold,  10  per  cent  of  palladium,  and  4  per  cent  of  silver  (44, 121}. 

When  the  gold  bars  from  Gongo-Soco,  Brazil,  first  began  to  come  to 
England,  the  Mint  refused  to  accept  them  because  of  their  brittleness 
The  famous  platinum  refiner  Percival  Norton  Johnson  assayed  them,  how 
ever,  detected  the  palladium,  and  perfected  a  process  for  refining  and 
toughening  the  Brazilian  gold  (51,  52).  In  1837  he  presented  specimens 
of  palladium-gold,  palladium  ammonium  chloride,  and  palladium  metal 
to  W.  A.  Lampadius  of  the  Freiberg  School  of  Mines.  According  to 
Lampadius,  "Palladium  has  not  been  separated  from  the  Brazilian  gold 
until  the  last  four  years,  but  since  that  time  Mr.  Johnson,  who  had  worked 
on  palladium  a  great  deal  with  the  late  Wollaston,  has  given  the  owners 
of  the  aforementioned  gold  mine  a  method  of  parting  by  means  of  which 
the  gold  is  produced  pure,  and  the  separated  palladium  put  to  many 
other  uses.  .  .  .  The  palladium  thus  produced,  alloyed  with  20  per  cent 
silver,  is  now  used  in  London  as  metal  for  dentists,  also  for  making  scales 
for  sextants  and  other  astronomical  instruments.  Alloyed  with  copper,  it 
gives  a  composition  which  makes  steel  more  elastic.  Even  earlier,  a 
watchmaker,  Bennet,  specified  an  alloy  of  24  palladium,  44  silver,  72  gold, 
and  92  copper  for  bearings  for  chronometers"  (52). 

Johnson  separated  the  palladium  from  an  enormous  quantity  of  the 
Gongo-Soco  gold,  and  in  1845  supplied  the  Royal  Geological  Society  of 


432  DISCOVERY  OF  THE  ELEMENTS 

London  with  a  sufficient  quantity  of  this  metal  for  the  casting  o£  the 
Wollaston  Medal  (44}.  Johnson  was  always  considerate  of  the  miners, 
and  sincerely  devoted  to  their  welfare.  He  spent  much  of  his  time  and 
fortune  on  the  schools  which  he  erected  near  the  mines  ( 51 ) . 

In  1809  Wollaston  demonstrated  the  presence  of  grains  of  native 
palladium  and  native  platinum  in  a  Brazilian  alluvial  gold  ore  presented 
to  him  by  the  Portuguese  ambassador,  EL  E.  Chev.  de  Souza  Coutinho. 
Wollaston  was  led  to  this  discovery  by  the  observation  that  some  of  the 
grains,  although  they  looked  like  platinum,  dissolved  faster  in  aqua  regia 
(44,  122,  123).  In  1825  Alexander  von  Humboldt  also  reported  the 
occurrence  of  native  palladium  in  Brazil  (109). 


RHODIUM 

W,  H.  Wollaston  discovered  rhodium  in  1803-04  in  crude  platinum 
ore.  Although  he  did  not  definitely  state  the  source  of  this  ore,  it  must 
have  come  from  South  America;  the  Russian  platinum  ores  had  not  yet 
been  discovered.  "Since  the  platina  to  be  procured  in  this  country/'  said 
Wollaston,  "generally  contains  small  scales  of  gold  intermixed,  as  well  as 
a  portion  of  the  mercury  which  the  Spaniards  employ  for  the  separation 
of  the  gold,  the  platina  used  for  my  experiments,  after  being  by  mechanical 
means  freed,  as  far  as  possible,  from  all  visible  impurities,  was  exposed  to 
a  red  heat  for  the  purpose  of  expelling  the  mercury"  (9). 

Dr.  Wollaston  dissolved  a  portion  of  crude  platinum  in  aqua  regia, 
and  neutralized  the  excess  acid  with  caustic  soda,  He  then  added  sal 
ammoniac  to  precipitate  the  platinum  as  ammonium  chloroplatinate,  and 
mercuric  cyanide  to  precipitate  the  palladium  as  palladious  cyanide. 
After  filtering  the  precipitate,  he  decomposed  the  excess  mercuric 
cyanide  in  the  filtrate  by  adding  hydrochloric  acid  and  evaporating  to 
diyness.  When  he  washed  the  residue  with  alcohol,  everything  dissolved 
except  a  beautiful  dark  red  powder,  which  proved  to  be  a  double  chloride 
of  sodium  and  a  new  metal  (3),  which,  because  of  the  rose  color  of  its 
salts,  Dr.  Wollaston  named  rhodium  (9).  He  found  that  the  sodium 
rhodium  chloride  could  be  easily  reduced  by  heating  it  in  a  current  of 
hydrogen,  and  that  after  the  sodium  chloride  had  been  washed  out,  the 
rhodium  remained  as  a  metallic  powder.  He  also  obtained  a  rhodium 
button, 

Thomas  Thomson  said  that  Dr.  Wollaston  had  amazingly  keen  vision 
and  remarkably  steady  hands.  He  could  write  on  glass  with  a  diamond 
in  clear,  well-formed  letters  which  were  so  small  that  other  persons  could 
read  them  only  with  a  microscope  (4). 

That  Berzelius  was  well  acquainted  with  Dr.  Wollaston  and  held  him 


THE  PLATINUM  METALS 


433 


in  high  esteem  may  be  seen  from  his  letter  to  Berthollet  written  in  London 
in  October,  1812: 

My  stay  here  [said  Berzelius]  has  been  most  interesting  and  instructive  in 
furnishing  me  a  quantity  of  chemical  resources  of  which  I  formerly  had  no  idea. 
But  what  I  value  most  of  all  is  the  personal  acquaintance  of  the  admirable  Wol- 
laston  and  the  brilliant  Davy.  I  am  sure  that  among  the  chemists  who  are  at 
present  in  the  prime  of  life  there  is  none  that  can  be  compared  with  Wollaston 
in  mental  depth  and  accuracy  as  well  as  in  resourcefulness,  and  all  this  is  com 
bined  in  him  with  gentle  manners  and  true  modesty  I  have  profited  more  by 
an  hour's  conversation  with  him  than  frequently  by  the  reading  of  large  printed 
volumes.  .  .  .  Simplicity,  clarity,  and  the  greatest  appearance  of  truth  are 
always  the  accompaniments  of  his  reasoning  (5). 


William  Hyde  Wollaston,  1766-1828. 
English  chemist  and  physicist  Dis 
coverer  of  palladium  and  rhodium  In 
ventor  of  a  process  for  making  platinum 
malleable.  Famous  for  "his  researches 
on  force  of  percussion,  gout,  diabetes, 
columbium  (niobium),  tantalum,  and 
titanium,  and  his  scale  of  chemical 
equivalents. 


In  the  diary  which  he  kept  on  this  visit  to  England,  Berzelius  wrote, 

Dr.  Wollaston,  Secretary  of  the  Royal  Society,  known  through  his  numer 
ous  discoveries  in  chemistry  and  physics,  is  a  man  between  forty  and  fifty  years 
old,  of  very  pleasant  appearance,  very  polished  manners,  plainness  and  clearness 
in  his  conversation,  interest  in  his  slightest  gesture,  and  with  such  a  spirit  of 
justice  and  gifted  with  such  moderation  in  his  views  that  it  has  become  a  com 
mon  proverb  that  whoever  argues  with  Wollaston  is  wrong  (30) . 

The  letters  of  Dr.  Alexandre  Marcet  to  Berzelius  give  us  a  pleasing 
picture  of  Dr.  Wollaston's  friendly  nature.  On  May  24,  1814,  Dr.  Marcet 
wrote: 


434  DISCOVERY  OF  THE  ELEMENTS 

Would  you  believe  it,  my  dear  friend,  that  while  your  kind  and  interesting 
letter  of  April  12th  was  on  its  way  to  London,  I  was  occupied  with  friend  Wol- 
laston  in  enjoying  all  the  dissipations  of  Paris  One  fine  morning,  near  the  end 
of  April,  Wollaston  came  into  my  house  and  said  to  me:  "I  have  cunous  news 
for  you"  "What!"  I  replied,  "Has  Bonaparte  returned  to  Paris?"  "No,"  he 
said,  "it  is  even  more  curious  than  that  ...  I  am  going  to  Pans  tomorrow, 
and'you  are  one  of  the  party."  I  rubbed  my  eyes,  thinking  I  was  dreaming, 
but  he  finally  proved  to  me  that  it  was  not  a  dream;  and  as  everything  Wollaston 
says  is  gospel  (Sir  John  Sebnght  has  nick-named  him  "The  Pope"),  I  immedi 
ately  told  my  wife  that  fate  was  calling  me  to  Paiis  for  a  fortnight,  gave  a  good 
dose  to  each  of  my  patients,  and  left  .  .  .  (10) . 

Sir  Edward  Thorpe  gives  quite  a  different  picture  of  Wollaston,  how 
ever,  when  he  says, 

He  resembled  Cavendish  in  temperament  and  mental  habitudes,  and,  like 
him,  was  distinguished  for  the  range  and  exactitude  of  his  scientific  knowledge, 
his  habitual  caution,  and  his  cold  and  reserved  disposition  (11). 

On  another  occasion  Dr.  Marcet  wrote,  "The  excellent  Wollaston  has 
just  lost  his  father,  who  leaves  a  large  fortune,  which  I  dare  to  reply,  will 
not  spoil  our  friend"  (12).  On  January  23,  1816,  he  suggested  in  reply  to 
a  question  asked  by  Berzelius, 

If  you  wish  to  send  Wollaston  a  piesent  in  the  name  of  the  prince,  the  only 
idea  that  comes  to  me  is  a  fine  hunting  gun  of  your  splendid  Swedish  steel.  The 
dear  Doctor,  pope  that  he  is,  has  taken  seriously  to  hunting,  and  already  acquits 
himself  with  much  success.  The  fact  is  he  does  not  know  how  to  do  anything 
poorly  (10). 

Dr.  Wollaston  was  a  man  of  very  broad  interests,  as  a  list  of  his 
publications  will  show.  His  papers  were  on  such  diverse  subjects  as: 
force  of  percussion,  fairy  rings,  gout,  diabetes,  seasickness,  metallic 
titanium,  the  identity  of  columbium  (niobium)  and  tantalum,  a  reflection 
goniometer,  micrometers,  barometers,  a  scale  of  chemical  equivalents, 
and  the  finite  extent  of  the  atmosphere.  He  died  in  London  on  December 
22,  1828  (13). 

In  1824  A.  M,  del  Rio  analyzed  a  gold-rhodium  alloy  from  the  parting- 
house  in  Mexico,  but  did  not  state  the  original  source  of  the  metal  (119). 
In  the  introduction  to  his  paper  he  stated:  "In  1810  Mr.  Cloud,  refiner 
(now  director)  of  the  mint  at  Philadelphia,  discovered  that  two  ingots 
from  Brazil  were  alloys  of  gold  with  palladium:  we  have  here  one  of 
gold  with  rhodium,  a  discovery  hitherto  unknown  in  Europe,  like  number 
less  other  remarkable  things  which,  under  the  auspices  of  liberty,  will  be 
brought  to  light  in  a  country  so  extensive  and  highly  favoured  by  nature" 
(119). 


THE  PLATINUM  METALS 


435 


From  Figuier's  "Vies  des  Savants  Illustres3 


Georges-Louis  Leclerc,  Comte  de  Button,   1707-1788. 

French  naturalist  famous  for  his  beautiful  literary  style. 
Founder  of  the  Jardin  des  Plantes.  Author  of  a  "Nat 
ural  History"  in  forty-four  volumes,  in  which  he  dis 
cussed  insects,  birds,  quadrupeds,  minerals,  the  theory 
of  the  earth,  and  the  epochs  of  Nature.  One  of  the 
first  to  investigate  platinum. 


436  DISCOVERY  OF  THE  ELEMENTS 

Rhodium  occurs  associated  with  platinum  ores,  and  also  in  the  mineral 
rhodite  in  the  gold-bearing  sands  of  Brazil  and  Colombia. 

OSMIUM  AND  IRIDIUM 

Smithson  Tennant,  the  discoverer  of  osmium  and  iridium,  like  Dr. 
Wollaston,  was  the  son  of  a  clergyman.  He  was  born  in  Wensleydale, 
near  Richmond,  Yorkshiie,  on  November  30,  1761.  At  the  age  of  nine 
years  he  had  the  misfortune  to  lose  his  father,  and  not  many  years  later 
he  witnessed  the  tragic  death  of  his  mother,  who,  while  riding  with  him, 
was  thrown  from  her  horse  and  instantly  killed.  Tennant's  elementary 
education  was  fragmentary,  but  even  when  very  young  he  was  fond  of 
reading  chemical  books  and  performing  experiments.  When  he  was  only 
nine  years  old  he  made  some  gunpowder  for  fireworks  (14). 

In  1781  he  went  to  Edinburgh  to  study  under  the  famous  chemist 
and  physician  Dr.  Joseph  Black,  and  in  the  following  year  he  entered 
Christ's  College,  Cambridge,  where  he  studied  chemistry,  botany,  mathe 
matics,  and  Newton's  "Principia."  His  room  at  college  was  a  scene  of 
confusion:  books,  papers,  and  chemical  apparatus  littered  the  floor,  and 
his  indolent  and  unsystematic  habits  were  indeed  a  serious  handicap 
throughout  his  scientific  career  (15). 

When  he  was  twenty-three  years  old,  he  traveled  through  Denmark 
and  Sweden,  where  he  met  the  famous  C  W.  Scheele,  and  for  the  rest  of 
his  life  he  delighted  in  showing  his  English  friends  the  minerals  that  the 
great  Swedish  chemist  had  given  him  on  thts  occason.  Tennant  also 
traveled  through  France  and  the  Netherlands  and  met  the  most  eminent 
chemists  of  those  countries.  Berzelius  said  that  Tennant  always  earned 
in  his  pocket  a  map  of  Sweden  which  had  become  worn  and  soiled 
through  years  of  use  and  that  he  spoke  French  "gladly  and  well"  (30). 
He  received  his  degree  of  Doctor  of  Medicine  from  Cambridge  in  1796, 
but  never  practiced. 

In  the  same  year  he  proved  by  an  ingenious  experiment  that  the 
diamond  consists  solely  of  carbon.  This  he  did  by  burning  a  weighed 
diamond  by  heating  it  with  saltpeter  in  a  gold  tube.  The  carbon  dioxide 
united  with  the  potash  in  the  saltpeter,  and  was  later  evolved.  Most 
chemists  would  have  felt  deep  concern  over  the  outcome  of  such  a  costly 
and  impoitant  experiment,  but  Tennant  went  horseback  riding  at  his  usual 
hour,  leaving  the  results  to  the  mercy  of  his  assistant.  However,  since 
the  assistant  was  the  gifted  William  Hyde  Wollaston,  the  outcome  was 
successful  (14, 16). 

In  1803  Tennant  found  that  when  crude  platinum  is  dissolved  in 
dilute  aqua  regia,  there  remains  a  black  powder  with  a  metallic  luster. 
This  had  been  observed  before  and  was  thought  to  be  graphite,  but 


THE  PLATINUM  METAX.S  437 

Tennant  investigated  it  carefully  in  an  attempt  to  alloy  lead  with  it,  and 
concluded  that  it  contained  a  new  metal  (17).  In  the  autumn  of  the  same 
year  H.-V.  CoDet-Descotils,  a  friend  and  pupil  of  N.-L.  Vauquelin,  found 
that  this  powder  contains  a  metal  which  gives  a  red  color  to  the  precipi 
tate  from  an  ammoniacal  platinum  solution  (18).  When  Vauquelin 
treated  the  powder  with  alkali  he  obtained  a  volatile  oxide  which  he 
believed  to  be  that  of  the  same  metal  with  which  Descotils  was  dealing 
(19). 

In  the  meantime  Tennant  continued  his  researches,  and  the  results 
which  he  communicated  to  the  Royal  Academy  in  the  spring  of  1804 
showed  that  the  powder  contains  two  new  metals,  which  may  be  separated 
by  the  alternate  action  of  acid  and  alkali.  One  of  these  he  named  indium 
because  its  salts  are  of  varied  colors,  and  the  other  he  called  osmium 
because  of  its  odor  (20). 

These  discoveries  may  best  be  described  in  his  own  words: 

Upon  making  some  experiments,  last  summer,  on  the  black  powder  which 
remains  after  the  solution  of  platina,  I  observed  that  it  did  not,  as  was  generally 
believed,  consist  chiefly  of  plumbago,  but  contained  some  unknown  metallic 
ingredients.  Intending  to  repeat  my  experiments  with  more  attention  during 
the  winter,  I  mentioned  the  result  of  them  to  Sir  Joseph  Banks,  together  with 
my  intention  of  communicating  to  the  Royal  Society  my  examination  of  this 
substance,  as  soon  as  it  should  appear  in  any  degree  satisfactory. 

Two  memoirs  were  afterward  published  in  France  [continued  Tennant] 
one  of  them  by  M.  Descotils  and  the  other  by  Messrs.  Vauquelin  and  Fourcroy. 
M.  Descotils  chiefly  directs  his  attention  to  the  effects  produced  by  this  sub 
stance  on  the  solution  of  platina.  He  remarks  that  a  small  portion  of  it  is  always 
taken  up  by  nitromuriatic  acid  during  its  action  on  platina;  and,  principally 
from  the  observations  he  is  thence  enabled  to  make,  he  infers  that  it  contains  a 
new  metal,  which,  among  other  properties,  has  that  of  giving  a  deep  red  colour 
to  the  precipitates  of  platina.  M.  Vauquelin  attempted  a  more  direct  analysis 
of  the  substance,  and  obtained  from  it  the  same  metal  as  that  discovered  by 
M.  Descotils,  But  neither  of  these  chemists  have  observed  that  it  contains  also 
another  metal,  different  from  any  hitherto  known.  .  .  . 

Tennant  gave  the  name  indium  to  the  metal  which  Descotils  and 
Vauquelin  had  observed,  and  the  name  osmium  to  the  new  one  (20). 
In  speaking  of  indium,  osmium,  paDadium,  and  rhodium,  W«  T.  Brande 
stated  in  his  lectures  in  1817,  uOf  these,  the  two  former  were  discovered 
by  the  late  Mr.  Tennant  and  the  two  latter  by  Dr,  Wollaston;  and  had  we 
searched  throughout  chemistry  for  an  illustrative  instance  of  the  delicacy 
of  the  modern  art  of  analysis,  it  would  be  difficult  to  have  found  any  one 
more  notorious  than  the  history  of  the  discovery  and  separation  of  these 
bodies  exhibits"  (46).  During  the  entire  course  of  the  researches  which 
led  to  the  discovery  of  these  four  metals,  Dr,  Wollaston  and  Tennant  had 
friendly  intercourse  with  each  other,  and  each  kept  in  close  touch  with 


438  DISCOVERY  OF  THE  ELEMENTS 

the  other's  work.    As  a  brief  relaxation  from  their  scientific  labors,  they 
visited  the  Giants'  Causeway  together. 

Smithson  Tennant  had  a  most  kind  and  forgiving  nature.  When  a 
dishonest  steward  on  his  estate,  who  had  become  so  heavily  in  debt  that 
Tennant  was  obliged  to  examine  the  accounts,  committed  suicide,  Tennant 
not  only  excused  the  unfortunate  family  from  the  payment  of  the  debt, 
but  assisted  them  financially  in  the  kindest  possible  manner  (14). 

Tennant,  like  Wollaston,  enjoyed  the  esteem  and  friendship  of  the 
great  Swedish  master,  Berzelius,  who  paid  him  a  visit  in  the  summer  of 
1812.  Together  they  rode  on  horseback  to  inspect  the  100-acre  experi 
mental  oat  field  in  which  Tennant  had  mixed  lime  with  the  soil  in  de 
creasing  ratio  from  one  end  to  the  other  (31).  After  he  had  shown 
Berzelius  the  tall,  well-developed  oats  at  the  highly  limed  end  and  the 
sickly  plants  at  the  other  end  of  the  field,  they  visited  the  limekiln  which 
Tennant  himself  had  designed  (30). 

Berzelius  may  perhaps  have  envied  the  English  chemist's  horseman 
ship,  for,  after  receiving  the  Cross  of  the  Order  of  the  Northern  Star,  he 
said  in  a  letter  to  Dr.  Marcet,  "Here  I  am  then  a  kind  of  cavalier,  I  whose 
manner  of  mounting  a  horse  Tennant  can  describe  to  you"*  (24).  In  a 
letter  to  J.  G.  Gahn,  Berzelius  wrote:  "Tennant  is  of  about  the  same  age 
as  Wollaston,  but  is  gray-haired  and  looks  like  an  old  man.  He  is  a 
charming  man,  gets  off  a  lot  of  droll  ideas  which  entertain  any  sort  of 
society,  scientific  or  otherwise,  He  is  a  rather  good,  reliable  chemist,  but 
doesn't  have  either  Wollaston's  or  Davy's  head;  and  now  he  has  lost  much 
of  his  memory,  so  that  one  can  tell  him  the  same  thing  on  two  successive 
days  with  full  assurance  that  it  will  be  new  to  him.  He  is  badly  dressed, 
is  careless  of  his  appearance,  and  makes  a  poor  showing.  His  chemicals 
are  so  helter  skelter  that  he  gets  permission  to  pull  out  all  the  table 
drawers  in  the  parlor  to  convince  himself  of  the  absence  of  what  one 
would  never  expect  to  find  except  in  a  laboratory"  (53). 

In  May,  1813,  Dr.  Marcet  wrote  to  Berzelius,  "Our  friend  Tennant 
has  just  been  elected  professor  of  chemistry  at  Cambridge  after  a  very 
long  struggle  with  a  candidate  who  had  many  friends.  His  position  de 
mands  that  he  give  twenty  lectures  a  year,  which  will  not  be  very  difficult 
for  him"  (22),  Berzelius  replied,  "Congratulate  Tennant  for  me  on  his 
new  profession  and  tell  him  that  we  expect  from  his  hands  the  life  of 
Newton  more  correct  than  we  have  yet  seen  it"  (23), 

Tennant  was  destined  to  give  his  lecture  course  at  Cambridge  only 
once,  for  his  life  was  cut  short  by  a  tragic  accident,  the  following  account 
of  which  was  written  by  Dr.  Marcet  to  Berzelius  on  March  29,  1815: 

*  "Me  voila  done  une  espece  de  chevalier,  moi,  dont  Tennant  peut  vous  apprendre 
comment  ie  monte  a  cheval." 


THE  PLATINUM  METALS  439 

You  have  doubtless  learned  of  the  tragic  death  of  poor  Tennant.  I  was 
often  on  the  point  of  writing  you,  but  the  grief  of  being  the  first  to  tell  you  this 
stoiy  restrained  me.  He  had  spent  six  months  in  France  and  was  returning 
loaded  with  curious  observations  in  geology,  chemistry,  political  economy,  etc. 
He  had,  it  is  said,  discovered  in  sea  water  the  source  and  origin  of  iodine.  He 
announced  himself  every  week  for  a  month  or  so,  and  nevertheless  did  not  come. 
Quite  like  himself,  he  clung  to  all  the  objects  along  the  way,  and  advanced  only 
very  slowly.  He  finally  arrives  at  Calais,  then  at  Boulogne,  and  after  having 
spent  about  fifteen  days  between  these  two  places  while  waiting  for  a  perfectly 
favorable  wind,  he  finally  sets  sail  But  a  calm  arises  and  they  are  obliged  to 
return  to  port.  Our  friend  seeks  to  console  himself  for  this  disappointment  by 
taking  a  horseback  ride,  he  proposes  to  a  Prussian  officer  who  was  on  board 
with  him  that  they  go  together  to  see  a  column  erected  to  Bonaparte  a  few 
miles  from  Boulogne. 

They  had  to  pass  over  a  little  draw-bridge  [continued  Dr  Marcet]  The 
officer  goes  over  first,  but  as  soon  as  he  is  on  the  bridge  he  notices  it  pivoting  on 
its  center  and  -that  it  is  going  to  open  into  the  ditch.  He  cries  to  Tennant, 
"Don't  come  any  farther,"  and  at  the  same  time  rushes  on  to  re-establish 
equilibrium,  but  it  was  too  late;  he  feels  that  another  force  is  pressing  on  the 
bndge  and  forcing  it  to  an  inclined  plane  ...  he  slides  back  with  his  horse 
and  falls  from  twelve  to  fifteen  feet  into  the  ditch.  Recovered  from  his  shock, 
he  looks  around  him  and  sees  poor  Tennant  lying  against  the  waU  at  the  end  of 
the  ditch  with  his  horse  writhing  on  top  of  him.  He  pushes  the  horse  away, 
lifts  our  friend,  .and  finds  him  dying.  .  .  .  Who  would  have  thought  that  our 
friend  would  die  while  visiting  a  work  of  war,  of  which  you  know  he  had  the 
greatest  horror  You  well  know,  and  I  have  no  need  to  tell  you,  all  that  his 
friends,  all  that  science,  have  lost.  He  was  a  unique  man  and  one  who  will 
probably  never  be  replaced.  He  loved  you  dearly,  and  I  know  you  will  mourn 
him  sincerely  (24). 

Tennant  had  "an  expressive,  intelligent  face  ...  an  intuitive  and 
prompt  perception  of  truth  ...  a  broad  mind,  deep  moral  feelings,  and 
a  zeal  for  the  improvement  of  mankind"  (15).  He  delighted  in  the 
artistic  achievements  of  Virgil,  Milton,  Pascal,  Gray,  Handel,  and  Raphael. 
His  never-failing  sense  of  humor  consisted  in  "fanciful  trains  of  Imagery, 
in  natural,  but  ingenious  and  unexpected,  turns  of  thought  and  expression, 
and  in  amusing  anecdotes,  slightly  tinged  with  the  ludicrous.  The  effect 
of  these  was  heightened  by  a  perfect  gravity  of  countenance,  a  quiet, 
familiar  manner,  and  a  characteristic  beauty  and  simplicity  of  language" 

(15). 

According  to  W.  T.  Brande,  Wollaston  also  discovered  "a  separate 
ore,  consisting  of  indium  and  osmium,  among  the  grains  of  crude  plati 
num.  Its  specific  gravity  is  19.5;  it  is  hard,  not  malleable,  and  very  bril 
liant"  (120, 124).  Osmium  occurs  in  laurite  and  in  osmiridium.  A  kind 
of  iridosmium  (osmiridium  high  in  indium)  called  trite  was  discovered 


440  DISCOVERY  OF  THE  ELEMENTS 

prior  to  1841  by  Hans  Rudolph  Hermann  in  the  gold  mines  of  the  Urals 
(125).    K.  K.  Klaus  stated  that  this  mineral  also  contained  3  per  cent  of 

ruthenium  (126). 

In  1805  Dr.  Wollaston  published  in  the  Philosophical  Transactions  an 
account  of  an  ore  of  indium  intermixed  with  grams  of  crude  platinum, 
which  could  be  dissolved  out  with  aqua  regia.  In  the  insoluble  portion 
of  the  ore  he  found  only  indium  and  osmium.  Although  Smithson  Ten- 
nant  was  prevented  by  his  fatal  accident  from  analyzing  the  mineral 
specimen  which  Wollaston  gave  him,  Thomas  Thomson  analyzed  it  in 
1826  and  found  it  to  consist  of  iridium,  osmium,  and  a  small  amount  of 
iron  (127). 

RUTHENIUM 

The  element  ruthenium  is  the  little  Benjamin  of  the  platinum  family. 
It  did  not  see  the  light  until  more  than  a  century  after  the  discovery  of 
platinum,  but,  to  avoid  separating  it  too  far  from  its  older  brothers,  its 
story  will  be  told  here. 

In  1828  Berzelius  and  G.  W.  Osann  (25),  professor  of  chemistry  at 
the  University  of  Dorpat,  examined  the  residues  left  after  dissolving 
crude  platinum  from  the  Ural  mountains  in  aqua  regia.  Berzelius  did 
not  find  in  them  any  unusual  metals  except  palladium,  rhodium,  osmium, 
and  iridium,  which  had  already  been  found  by  Wollaston  and  Tennant 
in  similar  residues  from  American  platinum.  Professor  Osann,  on  the 
other  hand,  thought  that  he  had  found  three  new  metals,  which  he  named 
pluranium,  ruthenium,  and  polinium  (25,  36).  In  1844,  however,  Pro 
fessor  Klaus,  another  Russian  chemist,  showed  that  Osann's  ruthenium 
oxide  was  very  impure,  but  that  it  did  contain  a  small  amount  of  a  new 
metal  (26,33). 

Karl  Karlovich  Klaus*  spent  his  infancy  and  boyhood  in  a  harsh, 
unkind  environment.!  He  was  born  in  the  Baltic-Russian  city  of  Dorpat* 
on  January  23,  1796.  His  father,  a  talented  painter  whose  pictures  later 
adorned  Klaus's  library,  died  in  1800.  Soon  after  her  husband's  death 
the  mother  married  another  artist,  and  she,  in  turn,  died  when  the  boy 
was  only  five  years  old.  Her  second  husband  soon  married  again,  and 
thus  the  little  boy  found  himself  a  strange  child  in  a  strange  home,  left 
without  affection  and  almost  without  care 


*  The  name  is  frequently  written  Carl  Ernst  Glaus      It  is  a  German  name,  not  a 

Russian  one. 

t  Most  of  the  details  regarding  the  life  of  Klaus  would  have  been  inaccessible  without 

the  kind  assistance  of  Mr.  M.  K.  Elias  of  the  Kansas  State  Geological  Survey,  who 

translated  B.  N.  Menshutlon's  biographical  sketch  from  the  Russian,     The  Author  is 

sincerely  grateful  to  him 

i  This  city  is  located  in  Estonia,  and  is  now  known  as  Tartu, 


THE  PLATINUM  METALS 


441 


Klaus  soon  showed  ability  in  design  and  sculpture,  and  his  love  for 
art,  poetry,  and  drama  helped  him  at  times  to  forget  the  none-too-gentle 
home  surroundings.  He  attended  the  grade  school  and  gymnasium  in 
Dorpat,  but  was  unable,  in  spite  of  his  excellent  record,  to  complete  the 
course  at  the  latter  institution.  However,  the  praise  given  by  his  teachers 
stimulated  him  to  further  efforts  which,  even  at  this  early  age,  revealed  the 
fundamental  features  of  his  character:  resoluteness,  optimism,  and  a 
desire  to  reach  at  any  cost  a  once-attempted  goal.  As  a  boy  he  enjoyed 
the  few  bright  aspects  of  his  cheerless  life,  and  as  an  adult  he  never 
complained  of  the  sufferings  of  his  childhood. 


Karl  Karlovich  Klaus,  1796-1864.  Pro 
fessor  of  pharmacy  and  chemistry  at  the 
Universities  of  Dorpat  and  Kazan,  He 
was  a  great  authority  on  the  chemistry  of 
the  platinum  metals. 


Courtesy  Mr   W.  D.  Trow 


When  forced  to  earn  his  own  living  at  the  age  of  fourteen  years,  he 
became  an  apprentice  in  a  pharmacy  in  St.  Petersburg.  Here  he  spent 
his  spare  moments  reading  books  on  chemistry,  pharmacy,  and  allied 
sciences.  These  attempts  at  self-education  were  so  successful  that  Klaus 
was  soon  able  to  pass  the  examinations,  first  for  assistant  pharmacist  and 
then  for  the  position  of  provisor  (36). 

In  1815  he  went  back  to  Dorpat,  passed  the  pharmacy  examinations 
at  the  University,  and  returned  to  the  St.  Petersburg  apothecary.  His 
study  of  the  natural  sciences  having  awakened  in  him  a.  desire  to  study 
Nature  at  first  hand,  he  went  to  Saratov  in  1817  as  provisor  of  a  pharmacy 
so  that  he  might  spend  his  leisure  hours  investigating  the  flora  and  fauna 
-of  the  Volga  steppes,  or  prairies,  in  eastern  Russia.  The  results  of  this 
ten-year  research  were  published  in  the  Russian  journals. 


442  DISCOVERY  OF  THE  ELEMENTS 

After  his  marriage  in  1821  Klaus  longed  to  have  an  apothecary  shop 
of  his  own,  and  five  years  later  he  began  business  in  Kazan,  where  he  soon 
had  the  best  pharmacy  in  the  town.  Here,  with  more  adequate  financial 
resources,  he  continued  his  study  of  the  flora  and  fauna.  He  soon  became 
recognized  as  an  authority  on  that  subject,  and  his  advice  was  sought 
whenever  a  scientific  expedition  was  to  be  sent  into  the  steppes,  This 
brought  him  into  contact  with  many  famous  scientists,  who  always  carried 
away  a  pleasant  recollection  of  his  modesty  and  willingness  to  cooperate. 
His  own  expedition  in  1827  through  the  region  between  the  Urals  and  the 
Volga  afforded  material  for  his  large  book  entitled  "Volga  Flora"  (36), 

When  an  assistantship  in  the  chemistry  depaitment  of  the  University 
of  Dorpat  was  offered  to  him  in  1831,  Klaus  sold  his  store  at  a  loss,  made 
the  long  trip  back  to  Estonia,  and  accepted  the  modest  position,  in  order 
to  devote  all  his  time  to  scientific  research.  While  completing  the  work 
for  his  master's  degree  in  chemistry,  he  found  time  to  explore  with 
Fr.  Gbbel  and  A.  Bergmann  the  Trans-Volga  salt  marshes  and  to  prepare 
all  the  sketches  for  a  large,  two-volume  record  of  the  expedition,  which 
was  published  at  Dorpat  in  1837  and  1838.  In  recognition  of  this  work 
they  were  awarded  the  Demidoff  prize  by  the  Academy  of  Science. 

Wishing  to  return  to  Kazan,  Klaus  applied  to  the  Secretary  of  Public 
Instruction  for  a  position  at  the  University.  The  Secietary  approved  the 
application,  but  only  after  listening  to  a  trial  demonstration  lecture  "On 
the  Shortest  Methods  for  Making  Chemicopharmaceutical  Preparations," 
which  Klaus  was  required  to  deliver  at  the  Medico-Surgical  Academy  of 
St,  Petersburg  (36).  Although  he  had  applied  for  a  position  in  the  depart 
ment  of  pharmacy  he  was  appointed  adjunct  in  chemistry. 

Upon  returning  to  Kazan  as  adjunct  in  chemistry,  he  entered  enthu 
siastically  into  the  work  of  remodeling  the  old  chemical  museum  into  a 
chemical  laboratory.  Klaus  also  succeeded  in  getting  six  additional  rooms 
in  a  newly  completed  university  building.  These  were  arranged  like 
Liebig's  laboratory  at  Giessen,  and  included  a  large  lecture  room,  well 
equipped  for  demonstration  experiments.  He  was  granted  an  appropria 
tion  of  about  10,000  rubles  ($5000)  for  the  purchase  of  glassware, 
reagents,  and  apparatus. 

In  1838  Klaus,  with  his  student  assistant  Kabalerov,  made  an  analysis 
of  the  water  from  the  Sergievsky  Mineral  Springs,  which  provided  the 
data  for  his  dissertation  for  the  doctorate  in  pharmacy.  Immediately  after 
receiving  this  degree,  he  was  made  extraordinary  professor  at  the  Uni 
versity,  and  six  years  later  he  was  promoted  to  the  position  of  ordinary 
professor. 

In  1840  Klaus  became  interested  in  platinum  residues.  The  reader 
will  recall  that  in  1828  Professor  G.  W.  Osann  of  Dorpat  University  had 
announced  the  presence  in  these  residues  of  three  new  metals,  the 


THE  PLATINUM  METALS  443 

existence  of  which  Berzehus  had  denied.  Professor  Klaus  wished  to  settle 
this  question,  and  the  first  step  in  his  investigation  was  a  careful  repetition 
of  Osann's  work.  He  obtained  two  pounds  of  platinum  residues  from 
P.  G  Sobolevskri,  a  platinum  lefiner  in  St.  Petersburg,  and  was  surprised 
to  find  that  they  contained  10  %  of  platinum,  besides  smaller  amounts  of 
osmium,  indium.,  palladium,  and  rhodium.  In  his  report  one  may  read, 

The  unexpected  richness  of  the  residues,  great  quantities  of  which  lie 
unused  at  the  laboratory  of  the  Government  Mint  at  St.  Petersburg,  appeared 
to  me  so  important  that  I  immediately  reported  the  results  of  my  investigation 
to  the  government  mining  authorities,  and  m  1842  I  went  to  the  capital  (36) . 

In  St.  Petersburg  he  interviewed  Count  Egar  F.  Kankrin,  the  Secretary 
of  the  Treasury  who  introduced  platinum  coinage  in  Russia,  Kankrin 
expiessed  complete  approval  of  Professor  Klaus's  investigation,  and 
Chevkin,  the  chief  of  the  staff  of  mining  engineers,  presented  him  with 
eighteen  pounds  (half  a  pood)  of  the  platinum  residues. 

The  working  of  these  residues  did  not  prove  as  profitable  as  Professor 
Klaus  had  hoped,  for,  as  he  said  in  1844: 

These  residues  were  poorer  than  the  first,  and  thus  my  hope  of  adapting] 
my  method  for  profitable  extraction  of  platinum  from  them  was  not  fulfilled. 
There  remained  only  an  investigation  interesting  for  science  Since  I  came  to 
realize  this  two  years  ago,  I  have  worked  constantly  on  this  hard,  prolonged, 
and  even  unhealthful  investigation;  now  I  report  to  the  scientific  world  the 
results  obtained:  (1)  results  of  analysis  of  rich  residues;  (2)  new  methods  for 
the  separation  of  the  metals  of  the  platinum  group,  (3)  methods  for  working 
up  poor  residues;  (4)  discovery  of  a  new  metal,  ruthenium;  (5)  results  of  the 
analysis  of  poor  residues  and  the  simplest  methods  of  decomposition  of  platinum 
ores  and  residues;  (6)  new  properties  and  compounds  of  the  previously  known 
metals  of  the  platinum  group.  All  this  may  serve  as  a  contribution  to  the 
chemical  history  of  a  precious  product  of  our  fatherland  (36). 

Klaus  obtained  six  grams  of  the  new  metal  from  osmiridium,  the 
portion  of  the  crude  platinum  which  is  insoluble  in  aqua  regia.  He 
calcined  a  mixture  of  osmiridium,  potash,  and  potassium  nitrate  in  a 
silver  crucible  placed  inside  a  Hessian  crucible  on  a  layer  of  magnesia 
(27) ,  After  heating  it  for  an  hour  and  a  half  at  bright  redness,  he  poured 
the  molten  contents  into  an  iron  capsule.  He  then  took  up  the  melt  in 
a  very  large  volume  of  water,  and  allowed  it  to  stand  four  days  in  the 
dark  in  a  completely  filled  bottle. 

The  orange-colored  solution,  containing,  among  other  things,  potas 
sium  ruthenate,  was  treated  with  nitric  acid,  whereupon  a  black  precipitate 
of  osmium  dioxide  containing  from  fifteen  to  twenty  per  cent  of  ruthenium 
oxide  was  thrown  down  as  a  velvety  deposit.  Klaus  distilled  this  with 
aqua  regia,  taking  care  to  condense  the  osmium  tetroxide.  The  residue 


444  DISCOVERY  OF  THE  ELEMENTS 

remaining  after  the  distillation  consisted  mainly  of  the  sesquichloride  and 
tetrachloride  of  ruthenium.  By  adding  ammonium  chloride,  Klaus  pre 
pared  ammonium  chlororuthenate,  (NH^RuCU,  a  salt  which  upon 
calcination  yields  spongy  ruthenium  ( 27,  38 ) . 

This  report,  which  was  entitled  "Chemical  investigation  of  the 
residues  of  Ural  platinum  ore  and  of  the  metal  ruthenium,"  occupied  one 
hundred  and  eighty-eight  pages  in  the  Scientific  Annals  of  Kazan 
University  for  1844.  In  the  following  year  it  was  published  in  book  form. 
For  patriotic  reasons  and  also  in  recognition  of  the  earlier  work  of  Pro 
fessor  Osann,  Klaus  retained  the  name  ruthenium,  which  means  Russia. 
The  white  substance  which  Osann  had  taken  for  the  oxide  of  this  new 
metal  consisted  chiefly  of  silicic  and  titanic  acids,  iron  peroxide,  and 
zirconia  (37).  Klaus  also  found  ruthenium  in  the  osmuidium  from  Ameri 
can  ores  (36,  128).  It  constituted  only  from  1  to  !1/2  per  cent  of  these 
residues  and  did  not  occur  in  the  portion  which  is  soluble  in  aqua 
regia  (126). 

When  Professor  Klaus  sent  a  sample  of  the  new  metal  to  Berzelius, 
the  great  Swedish  master  was  skeptical.  On  January  21,  1845,  he 
remarked  in  a  letter  to  F.  Wohler; 

Probably  Klaus's  experiments  on  the  residues  from  platinum  ores  and  on  the 
new  metal  ruthenium  have  already  been  described  in  the  German  journals.  He 
sent  me  his  paper  in  manuscript.  You  see  thereby  that  he  has  also  prepared 
colorless  salts  of  iridium  with  sulfurous  acid.  The  early  severe  winter  in 
November  interrupted  the  postal  communication  between  Ystad  and  Stralsund, 
so  that  I  have  not  received  the  German  journals  for  three  months  (28) . 

In  the  meantime  Klaus  continued  his  investigation  of  the  compounds 
of  ruthenium,  specimens  of  which  he  sent  to  Stockholm,  one  after  another, 
with  detailed  descriptions  of  their  properties  and  the  methods  of  prepara 
tion.  This  evidence  was  so  convincing  that  in  1845  Berzelius  announced 
in  the  Jahresbericht  his  acceptance  of  ruthenium  as  a  new  element  ( 36, 
37). 

On  March  9,  1846,  he  again  mentioned  Klaus's  paper  to  Wohler, 
saying: 

Klaus  in  Kazan  has  sent  me  a  resume^  [Nachernte]  concerning  ruthenium, 
which  I  expect  to  read  tomorrow  at  the  Academy  and  which  you  shall  then  re 
ceive  in  the  Ofversigten.  It  is  strange  that  he  does  not  publish  his  longer  paper. 
A  copy  of  it  has  been  in  my  hands  since  November,  1844,  Yet  he  surely  cannot 
have  intended  that  I  should  publish  it,  At  least  he  has  never  said  a  word 
about  it.  ... 

Berzelius  finally  suggested  to  Klaus  that  he  send  the  ruthenium  paper 
to  Wohler  for  publication  in  the  Annalen,  and  it  may  now  be  seen  in 
Volume  63  of  that  journal  (29,  38). 


Courtesy  Henry  M.  Leicester 

Alexander  Mikhallovich  Butlerov,  1828-1886.  Russian  organic  chemist. 
He  worked  with  K.  K.  Klaus  on  the  preparation  of  antimony  at  the 
University  of  Kazan  and  later  studied  organic  chemistry  under  N.  N. 
Zinin.  After  working  with  some  of  the  most  famous  chemists  in  Europe 
and  serving  as  professor  of  chemistry  at  the  University  of  Kazan  he  was 
appointed  ordinary  professor  of  chemistry  at  the  University  of  St. 

Petersburg,     See  ref.   (94). 


446 


DISCOVERY  OF  THE  ELEMENTS 


All  of  Klaus's  papers  on  the  platinum  metals  were  collected  and  pub 
lished  in  1854  in  a  Jubilee  Volume  issued  in  honor  of  the  fiftieth  anni 
versary  of  the  founding  of  the  University  of  Kazan.  He  continued  to 
teach  inorganic,  analytical,  and  organic  chemistry,  and  was  assisted  for 
a  time  in  the  organic  course  by  Nikolai  Nikolaevich  Zinin,  who  later 
became  the  founder  of  the  modern  school  of  organic  chemistry  in  Russia 
(93),  and  in  the  inorganic  course  by  Alexander  Mikhailovich  Butlerov 
(94). 

In  1852  Klaus  was  invited  to  occupy  the  chair  of  pharmacy  at  the 
University  of  Dorpat  and  to  take  charge  of  the  Pharmaceutic  Institute, 
at  that  time  the  only  institution  of  its  kind  in  all  Russia.  He  accepted 
the  appointment,  left  his  position  at  Kazan  in  charge  of  Butlerov, 
abandoned  the  long-cherished  steppes  of  the  Volga,  and  made  the  long 
trip  back  to  Estonia. 


J,  Henri  Debray,  1827-1888.  French 
chemist  who  collaborated  with  Henri 
Sainte-Claire  Deville  at  the  ficole  Nor- 
male  Sup£rieure  in  researches  on  gaseous 
dissociation.  He  also  investigated  beryl- 
hum,  molybdenum,  tungsten,  and  the 
metals  of  the  platinum  group,  and  made 
contributions  to  synthetic  mineralogy.  It 
was  in  Debray's  laboratory  that  Moissan 
liberated  fluorine. 


At  Dorpat  he  continued  his  investigation  of  the  platinum  metals  and 
their  alloys.  After  devoting  twenty  years  to  research  in  this  field,  he 
wished  to  publish  a  monograph  which  should  include  not  only  his  own 
researches  but  those  of  other  scientists.  In  1863  the  Russian  government 
sent  him  to  western  Europe  to  visit  the  laboratories  and  platinum  refineries 
and  to  study  the  history  of  the  platinum  metals  in  the  libraries  of  the 
great  scientific  centers.  Klaus's  achievements  were  so  well  known  that 
he  was  honored  wherever  he  went.  In  Berlin  he  met  Heinrich  and 
Gustav  Rose,  J.  G  Poggendorff,  and  Gustav  Magnus,  and  in  Paris  he 
studied  the  electric  furnaces  of  Henri  Sainte-Claire  Deville  and  H.  Debray 
(36). 


THE  PLATINUM  METALS  447 

Professor  Klaus  returned  to  Dorpat  in  January,  1864,  with  a  wealth 
of  material  for  the  monograph  on  the  platinum  group,  but  illness  unfortu 
nately  overtook  him,  and  the  work  was  never  completed.  He  passed 
away  on  March  24,  1864,  loved  and  respected  by  his  students  and 
colleagues.*  In  his  last  public  address  before  the  Pharmaceutical 
Society  of  St.  Petersburg,  he  emphasized  the  desirability  of  providing 
scholarships  for  needy  students  (36). 

In  1866  Friedrich  Wohler  discovered  a  ruthenium  mineral  When 
he  analyzed  the  shining  black  grains  of  what  seemed  to  be  an  unusual 
platinum  mineral  which  "Herr  Waitz  of  Cassel"  had  brought  back  from 
Borneo,  he  found  it  to  be  a  sulfide  of  ruthenium  and  osmium.  Wohler 
stated  that  this  mineral,  which  he  named  laurite,  presented  the  first 
example  of  the  natural  occurrence  of  sulfur  compounds  of  the  platinum 
metals  (129). 

LITERATURE  CITED 

( 1 )  PRIESTLEY,  J.,  "Experiments  and  Observations  on  Different  Kinds  of  Air," 

J.  Johnson,  London,  1774,  p.  xvii. 

(2)  DIXON,  JOSHUA,  "Biographical  account  of  William  Brownngg,  M  D.,"  Annals 

of  Phil,  10,  321-38,  401-17  (Nov.,  Dec  ,  1817) 

(3)  JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  Vol.  2,  Baudry  et  Cie ,  Paris,  1891, 

pp.  402-5. 

(4]     THOMSON,  THOMAS,  "History  of  Chemistry,"  Vol    2,  Colburn  and  Bentley, 
London,  1831,  pp   246-50 

(5)  SODERBAUM,  IL  G.,  t£Jac  Berzelius  Bref,"  Vol  1,  part  3,  Almqvist  and  Wiksells, 

Upsala,  1912-1914,  pp.  40-2. 

(6)  Ibid,  Vol.  1,  parts,  p.  47. 

(7)  WALLACH,  O.,  "Briefwechsel  zwischen  J.  Berzelius  und  F.  Wohler,"  Vol.  1, 

Verlag  von  Wilhelm  Engelmann,  Leipzig,  1901,  p.  253. 

(8)  "Reward  of  twenty  pounds  for  the  artificial  production  of  palladium,"  Nichol 

sons  ] ,  7,  75  (Jan.,  1804);  R.  CHENEVEX,  "Enquiry  concerning  the  nature 
of  a  metallic  substance  lately  sold  in  London  as  a  new  metal,  under  the 
title  of  palladium,"  ibid.,  7,  85-101  (Feb.,  1804),  176-82  (Mar.,  1804), 
Letter  from  Wollaston  to  Nicholson  concerning  Pd,  ibid ,  10,  204^-5  (Mar., 
1805),  T.  THOMSON,  "History  of  Chemistry,"  ref.  (4),  Vol.  2,  p.  217. 

(9)  WOIXASTON,  W.  H.,  "On  a  new  metal  found  in  crude  platina,"  Nicholson's  ]., 

(2)  10,34-42  (Jan,  1805). 

(10)  SODERBAUM,  H.  G.,  "Jac.  Berzehus  Bref,"  ref.  (5),  Vol  1,  part  3,  p.  98. 

1 II )  THORPE,  T  E  ,  "History  of  Chemistry,"  Vol.  1,  G.  P.  Putnam's  Sons,  London, 

1909-1910,  p.  114. 

(12)  SODERBAUM,  H.  G.,  "Jac  Berzehus  Bref,"  ref.  (5),  Vol   1,  part  3,  pp.  128-9. 

(IS)  POGGENDORFF,  J  C.,  "Biographisch-Literarisches  Handwbrterbuch  zur 
Geschichte  der  exakten  Wissenschaften,"  6  vols.,  Verlag  Chemie,  Leipzig 
and  Berlin,  1863-1937.  Articles  on  Wollaston,  Claus,  and  Scahger. 

(14)     THOMSON,  T  ,  "History  of  Chemistry,"  ref.  (4),  Vol  2,  pp.  232-40, 

*  According  to  the  Russian  (Julian)  calendar  Klaus  was  born  on  Jan.  11,  1796,  and 
died  on  March  12,  1864. 


448  DISCOVERY  OF  THE  ELEMENTS 

(15)  "Some  account  of  the  late  Smithson  Tennant,  Esq.,"  Annals  of  Phil ,  6,  1-11 

(July,  1815);  81-100  (Aug,,  1815);  Gentleman's  Mag.,  117,  281  (Mar., 
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(16)  TENNANT,  S.,  "On  the  nature  of  the  diamond,"  Nicholson's  }.,  I,  177-9  (July, 

1797), 

(17)  "Discovery  of  two  new  metals  in  crude  platina  by  Smithson  Tennant,  Esq , 

F.R.S  ,"  ibid.,  8,  220-1  (July,  1804). 

(IS)  COLLET-DESCOTILS,  H  -V.,  "On  the  cause  of  the  different  colours  of  the  triple 
salts  of  platina,  and  on  the  existence  of  a  new  metallic  substance  in  the 
metal,"  Nicholsons  /.,  8,  118-26  (June,  1804). 

( 19 )  VAUQUELIN,  N.-L.,  "Memoire  sur  riridium  et  1' osmium,  metaux^qui  se  trouvent 

dans  le  residu  insoluble  de  la  mine  de  plabne,  traitee  par  Tacide  nitromu- 
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(20)  TENNANT,  S.,  "On  two  metals,  found  in  the  black  powder  remaining  after 

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( 21 )  WHITE,  A.  M.  and  H.  B  FRIEDMAN,  "On  the  discovery  of  palladium,"  /.  Chem 

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(22)  SQDERBAUM,  H.  G.,  "Jac.  Berzelius  Bref,"  ref.  (5),  Vol.  1,  part  3,  p.  46. 

( 23 )  Ilnd.,  Vol.  1,  part  3,  p.  61. 

(24)  Ibid ,  Vol.  1,  part  3,  pp.  117-9. 

(25)  "New  metals  in  the  Urahan  platina,"  Phil.  Mag,  2,  391  (Nov.,  1827). 

(26)  BROWN,  J   C.,  "History  of  Chemistry,"  P.  Blakiston's  Son,  Philadelphia,  1913, 

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(27)  JAGNAUX,  R.,  "Histoire  de  la  Chirme,"  ref.  (3),  Vol.  2,  pp.  406-7. 

(28)  WALLACH,  O.,  "Bnefwechsel  zwischen  J.  Berzelius  und  F.  Wohler,"  ref.  (7), 

Vol.  2,  p.  520 

(59)     Ibid.,  Vol   2,  p.  580 

(30)  "Aus  Berzehus's  Tagebuch  wahrend  seines  Aufenthaltes  in  London  im  Sommer 

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(32)  ST.  JOHN,  "The  Lives  of  Celebrated  Travellers,"  Vol.  2,  J.  &  J.  Harper,  New 

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(34)  DIMTTRY,  "A  king's  gift,"  Mag.  Am.  History,  16,  308-16  (Oct,  1886). 

(35)  OGBURN,  S.  C.,  "The  platinum  metals,"  J.  Chem.  Educ,  5,  1371-84  (Nov., 

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(86)  MENSCHUTKIN,  B.  N.,  "Karl  Karlovich  Klaus,"  Ann  inst.  platine  (Leningrad), 
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(37)  "On  the  new  metal  ruthenium,"  Phil  Mag,,  (3),  27,  230-1  (Sept.,  1845). 

(38)  KLAUS,  K.  K.,  "Mine  de  platme,  osmium,  ruth6nium,"  J.  Pharm.  Chim.,  (3), 

8,  381-5  (Nov.,  1845);  "Beitrage  zur  Chemie  der  Platinmetalle,"  Ann.,  63, 
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(39)  FARABEE,  W.  C.,  "A  golden  hoard  from  Ecuador,"  Museum  Journal,  Univer 

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(40)  BEHGS^E,  P,  "The  Metallurgy  of  Gold  and  Platinum  among  the  pre-Colum 

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(41 )  KOPP,  H.,  "Geschichte  der  Chemie/'  Vol.  4,  Vieweg  und  Sohn,  Braunschweig, 

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(42)  SCHEFFER,  H.  T.,  "Das  weisse  Gold  oder  siebente  MetalL,  in  Spamen  Platina 

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(43)  PELLETIER,  BERTRAND,  "Memoires  et  observations  de  Chimie/'  Vol.  2,  Paris, 

1798  (an  VI),  pp,  120-133.  "Rapport  fait  au  Bureau  de  Consultation  sur 
les  Moyens  proposes  par  M.  Jeanety  pour  travailler  le  platine  (Juillet, 
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(44)  HUSSAK,  EUGEN,  ""tfber  das  Vorkommen  von  Palladium  und  Platin  IB  Brasi- 

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(50)  SMITH,  E.  F.,  "Chemistry  in  Old  Philadelphia/'  J.  B.  Lippincott  Co,  Phila 

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( 54 )  "Juhi  Cassaris  Scaligeri,  Exotericarum  exercitationum  Liber  XV  de  Subhlitate 

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450  DISCOVERY  OF  THE  ELEMENTS 

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(62)  TOWNSEND,  JOSEPH,  "A  Journey  through  Spain  in  the  Years  1786-7,"  3rd  ed  , 

Vol.  2,  James  Moore,  Dublin,  1792,  pp.  152-3. 

(63)  STEPHEN-,  LESLIE,  "Dictionary  of  National  Biography,"  Vol.  7,  Smith,  Elder 

and  Co.,  London,  1886,  pp.  85-6     Article  on  Browrmgg  by  G,  T.  Bettany 

(64)  Obituary  of  Brownrigg,  Gentleman's  Mag,  70,  386-S  (1800). 

(65)  WATSON,  WILLIAM,   "Several  papers   concerning   a  new   semi-metal   called 

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( 66 )  "Discurso  del  Ilmo.  Sr.  D.  Juan  Fages  y  Virgili,"  Establecirmento  Tipografico  y 

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(67)  LEWIS,  WILLIAM,  "Experimental  examination  of  a  white  metallic  substance 

said  to  be  found  in  the  gold  mines  of  the  Spanish  West  Indies  .  .  .  /*  Phil. 
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(68)  CRONSTEDT,  A.  F.,  "Aminnelse-tal  ofver  .  .    .Henric  Theoph.  Scheffer/'  Lars 

Salvius,  Stockholm,  1760,  31  pp 

(69)  KOPP,  H,  "Geschichte  der  Chemie,"  Vol.  4,  Fr.  Vieweg  und  Sohn,  Braun 

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(70)  VON  CRELL,  L.,  Review  of  Baron  von  Sickingen's  "Versuche  liber  die  Platina," 

Cr ell's  Neueste  Entdeckungen,  6,  197-206  (1782). 

(71 )  HOWE,  J  L  ,  "Bibliography  of  the  metals  of  the  platinum  group,  1748-1896," 

Smithsonian  Miscellaneous  Collections,  38,  1-318  (1897). 

(72)  HOWE,  J  L,  "Chabaneau*     an  early  worker  on  platinum,"  Pop.  Sci.  Mo.,  84, 

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(73)  QUENNESSEN,   Loxns,   "A  propos   de  Fhistoire   du   platine     Pierre   Frangois 

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(74)  MAFFEI,  E.  and  R.  RUA  FIGTJEROA.,  "Apuntes  para  una  Biblioteca  Espanola  .  .  . 

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( 75 )  "El  primer  centenario  de  Fausto  de  Elhuyar,"  Anales  Soc.  Espan  de  Fisica  y 

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(76)  DE  GALVEZ-CANERO,  A.,  "Apuntes  Biogr&ficas  de  D.  Fausto  de  Elhuyar  y  de 

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(77)  DrEBGART,  PAUL,  "Bertrage  aus  der  Geschichte  der  Chemie  dem  Gedachtnis 

von  G.  W.  A.  Kahlbaxim,"  Franz  Deuticke,  Leipzig  and  Vienna,  1909,  p 
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(78)  PELLETDER,  CHARLES  and  SEDILLOT,  JEX^E,   "Memoires  et  Observations  de 

Chimie  de  Bertrand  Pelletier,"  Vol.  2,   Croullebois,   Fuchs,  Barrois,   and 
Huzard,  Paris,  1798,  pp.  120-33. 

( 79  )     CrelTs  Ann,,  14,  53-4  ( 1790 ) 

(SO)     LACROIX,  ALFRED>  "Figures  de  Savants,"  Vol   2,  Gauthier-Villars,  Paris,  1932, 
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( 8 1 )  HARE,  ROBERT,  "Account  of  the  fusion  of  strontites  and  volatilization  of  plati 

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(82)  SMITH,  E   P.,  "Life  of  Robert  Hare,"  J.  B   Lippincott  Co.,  Philadelphia  and 

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THE  PLATINUM  METALS  451 

(83)  SODERBAUM,  H    G.,  ref.  (5),  Vol.  13,  p    132.     Letter  of  Berzehus  to  E    Mit- 

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(84)  "Laboratory  of  powder  metallurgy  established  at  Stevens  Institute  of  Technol 

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(85)  "Russian  coinage  of  platina,"  Phil   Mag    (2),  4,  458  (Dec.,  1828) 

(86)  KELLY,  F.  C  ,  "Powder  metallurgy"  Sci  Mo.,  57,  286-8  (Sept,  1943). 

(87)  WEEKS,  M   E.,  "Don  Jose  Celestmo  Mutis,  1732-1808,"  J.  Chem.  Educ.,  21, 

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(88)  FERGUSON,  ELSIE  G,  "Bergman,  Klaproth,  Vauquehn,  Wollaston,"  /    Chem, 

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( 89 )  DELEPINE,  MARCEL,  "Joseph  Pelletier  and  Joseph  Caventou,"  J.  Chem.  Educ  , 

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(90)  BROWNE,  C   A.,  "The  past  and  future  of  the  History  of  Chemistry  Division," 

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(91)  MENSCHUTKTN,  B.  N.,  "Discovery  and  early  history  of  platinum  in  Russia," 

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(92)  PROF    KLENCKE,   "Alexander  von  Humboldt.     A  Biographical  Monument," 

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(93)  LEICESTER,  HENRY  M.,  "N,  N.  Zinin,  an  early  Russian  chemist/'  J.  Chem. 

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( 94 )  LEICESTER,  HENRY  M  ,  "Alexander  Mildiailovich  Butlerov,"  ibid.,  17,  203-9 

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( 95 )  BRONK,  DETLEV  W  ,  "Joseph  Priestley  and  the  early  history  of  the  American 

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(96)  CORTENOVIS,  A.  M,  "Dissertation  sur  le  platine,  dans  laquelle  on  demontre 

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(97)  LIPPMANN,   E.    O    VON,   "Entstehung  und  Ausbreitung   der   Alchemic,"   J. 

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( 98 )  "Contributions  towards  the  chemical  knowledge  of  mineral  substances,  by  the 

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(99)  BERTHELOT,  M,  "Sur  les  metaux  egyptiens:     Presence  du  platme  parmi  les 

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(100)  LUCAS,  A,  "Ancient  Egyptian  Materials  and  Industries,"  2nd  ed ,  Edward 

Arnold  and  Co ,  London,  1934,  p   202 

(101 )  SCHWEJGGER,  J.  S.  C  ,  "Ueber  Platina,  Altes  und  Neues,"  J.  prate.  Chem ,  34, 

385-420  (1845) 

(102)  MOROS,  F    A.,  "Minerales  y  mineralogistas   espaiioles,"  Revista  real  acad. 

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(103)  BOSTOCK  and  RILEY,  "The  Natural  History  of  Pliny,"  VoL  6,  George  Bell  and 

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(104)  CRELL,  L.  VON,  "Ueber  die  Platina  die  den  Alten  schon  bekannt  war,     Von 

P.  Don  Ant   Mar.  Cortinovis  [sic]"  Crell's  Ann,  25,  166-7  (1796). 

(105)  LEWIS,  WILLIAM,  "The  Chemical  Works  of  Caspar  Neumann,  M.D  /*  W. 

Johnston,  G.  Keith,  etc ,  London,  1759,  pp    43-4. 

(106)  BERNAYS,  JACOB,  "Joseph  Justus  Scaliger,"  Wilhelm  Hertz,  Berlin,  1855,  pp, 

31-104. 


452  DISCOVERY  OF  THE  ELEMENTS 

(107)  NETTLESHIP,  HENRY,  "Essays  by  the  Late  Mark  Pathson,"  Vol.  1,  Clarendon 

Press,  Oxford,  1889,  pp  132-7,  154  Article  on  Joseph  Scahger,  reprinted 
from  Quarterly  Review,  108,  34  (July,  1860);  same  article  in  Living  Age, 
66,  579 

(108)  ROBINSON,  GEORGE  W  ,  "Autobiography  of  Joseph  Scahger,"  Harvard  Univer 

sity  Press,  1927,  128  pp, 

(109)  HUMBOLDT,  A.  VON,  "Ensayo  politico  sobre  Nueva  Espana,"  Vol  3,  Lecointe, 

Pans,  1836,  pp   46-9,  275-6. 

(110)  LUMB,  A.  D  ,  "The  Platinum  Metals,"  John  Murray,  London,  1920,  pp.  55-6 

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pp    144-6 

BEJARANO,  D.  M  M.,  "Diccionario  de  escntores,  maestros,  y  oradores  natural 
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THE  PLATINUM  METALS  453 

(129)  WOHLER,  F.,   "Ueber  ein  neues  Mineral  von  Borneo/7  Ann.,    139,    116-20 

(1866), 

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From  Li  Ch'iao-p'ing's  "Chemical  Arts  of  Old  China" 

Drawing  Up  Sea  Water  for  Making  Salt.    Salt  was  an  important  commodity 
to  the  ancient  Chinese.    They  used  several  processes3  one  o£  wliicli  was  the 

evaporation  of  sea  water. 


"How  is  it  then  that  from  the  fern 
Both  ash  and  clearest  glass  is  made 
By  those  most  learned  in  the  trade: 
Can  simple  depurations  turn 
The  fern  to  glass?    Glass  is  not  fern 
Nor  does  the  fern  exist  in  glass''  (28). 


17 

Some  old  potassium  and  sodium  compounds 

Long  before  sodium  and  potassium  metals  were  isolated,  many 
of  their  compounds  were  in  common  use.  Among  the  most  im 
portant  of  these  were  potash  (potassium  carbonate),  cream  of 
tartar,  saltpeter,  alum,  common  salt,  Glaubers  salt,  and  soda 
(sodium  carbonate).  Both  potash  and  soda  have  been  used  since 
ancient  times  in  the  manufacture  of  glass. 

Potash  from  Vegetable  Ash.  Dioscorides  Pedanios  knew  that  a 
soluble  substance  can  be  leached  out  of  wood  ashes  with  water,  but  did 
not  tell  how  to  prepare  it  in  solid  form  (1).  Haudicquer  de  Blancourt, 
in  his  book  on  "The  Art  of  Glass"  (1697),  described  the  preparation  of 
potassium  carbonate  from  the  ash  of  the  fern  and  other  plants,  "The  daily 
Experience  of  Salt  of  Fern  in  the  Glass-Houses"  said  he,  "assures  us  of 
its  usefulness  in  making  Glass.  It  grows  (in  France)  in  great  abundance 
in  the  woods  and  among  the  Mountains.  .  .  .  You  will  have  from  it  very 
good  ashes,  from  which  .  .  -  may  be  extracted  a  fine  and  good  salt; 
which  being  afterward  purified,  with  it  and  Tarso,  or  very  fine  Sand,  a 
Fritt  may  be  made  which  will  yield  a  very  fair  Crystal,  much  better  than 
the  ordinary,  and  [it]  will  be  strong  and  bend  much  more  than  one  would 
conceive  the  nature  of  Crystal  would  permit  .  .  ."  (2). 

Primitive  peoples  sometimes  used  the  ashes  of  certain  plants  as  a 
condiment  in  place  of  salt.  Some  of  the  American  Indians  in  Virginia 
used  the  ash  of  the  saltwort;  the  Delawares,  Iroquois,  Wyandots,  Chero- 
kees,  Chickasaws,  and  Creeks  seasoned  and  preserved  their  meats  with 
clean  wood  ashes  (3,  4).  The  Medical  Repository  for  1804  mentions  a 
similar  custom  among  the  natives  of  Bengal:  "In  the  seventh  volume  of 
the  Asiatic  Researches  is  a  paper  by  Surgeon  John  Macrae  on  the  manners 
and  customs  of  the  Cucis,  Kookies,  or  Lunctas,  a  race  of  people  that  live 
among  the  mountains  to  the  northeast  of  the  Chittagong  province  in  India. 
Of  this  peculiar  nation  he  relates  a  fact  which  corresponds  with  the 
practice  described  in  Medical  Repository,  Hexade  I,  volume  vi,  p.  330, 
among  American  Indians,  of  using  pure  and  fresh  wood-ashes  in  lieu  of 
sea-salt,  as  a  condiment  with  animal  food.  .  .  .  The  hunter,  ...  in 
his  excursions  through  the  forests,  boils  his  food  in  a  particular  kind  of 
bamboo.  From  the  ashes  of  a  different  species  of  the  same  plant,  he 
extracts  a  substitute  for  salt  to  eat  with  his  victuals  ,  .  ."  (4). 

455 


456  DISCOVERY  OF  THE  ELEMENTS 

Origin  of  Potash  in  Plants.  Early  chemists  disagreed  as  to  the  origin 
of  the  vegetable  alkali.  Louis-Claude  de  Bourdelin  (1696-1777)  and 
others  maintained  that  it  pre-existed  as  a  salt  in  the  living  plant  and 
that  the  combustion  merely  liberated  it  (5,  6).  Paracelsus,  Andreas 
Libavius,  Urban  Hiarne,  and  other  distinguished  chemists  also  believed 
in  the  pre-existence  of  this  alkali  in  the  plant  (S).  Others,  including 
Robert  Boyle,  Nicolas  Lemery,  J.  J,  Becher,  G.  E.  Stahl,  Johann  Kunckel, 
Etienne-Frangois  Geoffrey,  and  Herman  Boerhaave,  believed  that  the 
vegetable  alkali  was  produced  only  during  the  combustion  (5). 

Boerhaave  even  stated  in  his  "Elements  of  Chemistry"  that  "all  the 
vegetables  which  have  grown  on  the  earth  since  the  beginning  of  the 
world  to  the  present,  and  which  have  putrefied  without  being  reduced 
to  ash  by  the  action  of  fire,  and  have  been  consumed  in  the  course  of 
time,  have  never  yielded  a  single  grain  of  fixed  alkaline  salt.  On  the 
contrary,  they  have  been  dispersed  in  volatile  particles  .  .  ."  (7). 

In  1755  Joseph  Black  explained  why  alkali  freshly  leached  from 
vegetable  ash  is  so  caustic  and  why  it  becomes  milder  on  exposure  to 
air.  "It  never  appears,"  said  he,  "until  the  subject  be  converted  into  ashes, 
and  is  supposed  to  be  formed  by  the  fire,  and  to  be  the  result  of  a  par 
ticular  combination  of  some  of  the  principles  of  the  vegetable,  one  of 
which  principles  is  air,  which  is  contained  in  large  quantity  in  all  vegetable 
matters  whatever.  But,  as  soon  as  the  smallest  part  of  a  vegetable  is 
converted  into  ashes,  and  an  alkali  is  thus  formed,  this  salt  necessarily 
suffers  a  calcination,  during  which  it  is  kept  in  a  spongy  form  by  the 
ashes>  and  shows  a  very  considerable  degree  of  acrimony,  if  immediately 
applied  to  the  body  of  an  animal;  but  if  the  ashes  are  for  any  time  exposed 
to  the  air,  or  if  we  separate  the  alkali  from  them  by  the  addition  of  a  large 
quantity  of  water  and  subsequent  evaporation,  the  salt  imbibes  fixed  air 
[carbon  dioxide]  from  the  atmosphere,  and  becomes  nearly  saturated 
with  it;  tho?,  even  in  this  condition,  it  is  generally  more  acrid  than  salt 
of  tartar  [pure  potassium  carbonate],  when  this  is  prepared  with  a  gentle 
heat"  (5). 

In  1770  C.  W.  Scheele  showed  that  the  natural  product  cream  of 
tartar  is  a  salt  with  a  vegetable  alkaline  base  ( potash )  supersaturated  with 
a  vegetable  acid  ( tartaric } .  When  he  dissolved  cream  of  tartar  [potassium 
acid  tartrate]  in  boiling  water  -and  added  powdered  chalk  to  the  solution, 
the  limp  combined  with  part  of  the  tartaric  acid  and  gave  a  copious  white 
precipitate.  On  evaporating  the  supernatant  liquid  he  obtained  crystals 
of  "soluble  tartar"  [normal  potassium  tartrate]  (9,  10). 

G.-F.  Rouelle,  A.  S.  Marggraf,  and  others  showed  experimentally  that 
potash  can  be  extracted  from  plants  without  the  use  of  fire  (11 ) .  In  1764 
Marggraf,  for  example,  prepared  saltpeter  by  treating  tartar  with  nitric 
acid.  Since  saltpeter  was  known  to  contain  the  vegetable  alkali,  the  latter 


SOME  OLD  POTASSIUM  AND  SODIUM  COMPOUNDS  457 

must  have  pre-existed  in  the  plant  (5).  Although  J.  H.  Pott  had  stated 
definitely  that  the  vegetable  alkali  is  produced  only  by  burning  plants, 
an  editorial  note  in  Cretts  Neues  chemisches  Archiv  for  1785  stated  that 
the  incorrectness  of  this  statement  had  been  adequately  demonstrated  by 
Marggraf  and  Wiegleb  (12). 

P,-J.  Macquer  pointed  out  in  his  "Dictionary  of  Chemistry"  (1778) 
that  when  plants  are  decomposed  without  combustion,  acidic  substances 
such  as  tartar  and  potassium  acid  oxalate  are  produced,  that  plants  from 
which  these  acidic  substances  have  been  removed  by  extraction  or  dis 
tillation  yield  much  less  vegetable  alkali  than  they  otherwise  would;  that 
by  ignition  tartar  can  be  converted  almost  completely  to  this  alkali 
(potassium  carbonate);  that  tiae  alkali  in  vegetable  ash  is  therefore 
produced  by  the  combustion  of  this  acidic  substance;  that  decayed  wood, 
in  which  the  plant  acids  have  been  destroyed  by  fermentation,  yields 
scarcely  any  alkali  (as  Boerhaave  had  observed);  and  that  plants  con 
taining  little  or  no  acid  yield  on  combustion  little  or  no  vegetable  alkali 
(5). 

Although  Macquer  s  explanation  is  correct,  A.-L.  Lavoisier  still  held 
to  the  more  conservative  opinion.  In  his  "Elementary  Treatise  on  Chem 
istry,"  which  was  first  published  in  1789,  he  explained  the  formation  of 
potassium  carbonate  in  vegetable  ash  as  follows:  "As  the  potash  is  not 
formed,  or  at  least  not  liberated,"  said  he,  "except  as  the  carbon  of  the 
plant  is  converted  into  carbonic  acid  by  the  addition  of  oxygen,  either 
from  the  air  or  from  the  water,  the  result  is  that  each  molecule  of  potash, 
at  the  moment  of  its  formation,  finds  itself  in  contact  with  a  molecule  of 
carbonic  acid,  and  since  there  is  great  affinity  between  these  two  sub- 
stances,  combination  must  take  place"  (13). 

Lavoisier  realized  that  potash  is  present  in  the  ash  of  all  plants,  but 
he  was  not  convinced  of  its  pre-existence  in  the  living  organism.  "There 
are  no  vegetables,"  said  he,  "which  do  not  yield  more  or  less  potash  on 
incineration.  .  .  .  One  can  scarcely  doubt  that  the  ash,  or  in  other  words 
the  earth  which  plants  leave  when  one  burns  them,  pre-existed  in  those 
vegetables  before  the  combustion;  this  earth  apparently  forms  the  bony 
part,  or  skeleton  of  the  plant.  But  it  is  not  the  same  with  the  potash. 
No  one  has  yet  succeeded  in  separating  this  substance  from  plants  except 
by  using  methods  or  intermediates  which  can  provide  oxygen  or  nitrogen, 
such  as  combustion  or  combination  with  nitric  acid;  thus  it  has  not  been 
proved  that  this  substance  is  not  a  product  of  these  operations"  (13). 

In  1789  Dr  M.  Wall  of  Oxford,  recalling  Scheeles  experiments  on 
tartar,  added  some  "Glauber's  spirit  of  nitre"  to  cream  of  tartar  dissolved 
in  boiling  water.  By  careful  evaporation  of  the  solution,  he  obtained 
well-formed  crystals  of  niter  (saltpeter),  He  concluded  that  cream  of 


458  DISCOVERY  OF  THE  ELEMENTS 

tartar  "is  not,  as  has  been  commonly  supposed,  a  peculiar  acid,  joined 
with  impurities,  but  that  it  is  really  a  compound  salt,  containing  an  alkali 
joined  with  an  acid;  and  further,  that  the  alkaline  salt,  obtained  from 
tartar  by  incineration,  is  not  generated  in  the  fire,  but  was  actually  pre~ 
existent  in  the  tartar"  (9). 

A.-F.  de  Fourcroy  stated  in  1806:  "The  exact  nature  of  potash  is 
not  known:  it  was  formerly  believed  to  have  been  formed  from  lime  and 
nitrogen,  because  it  is  often  found  mixed  with  this  earth  in  vegetables, 
but  this  is  still  merely  a  hypothesis  which,  during  the  fifteen  years  since 
I  proposed  it,  has  not  been  proved  by  any  positive  fact"  (14). 

Potash  prepared  in  Hungary  by  leaching  wood  ashes  was  shipped 
to  the  glassblowers  and  soapmakers  in  Austria,  Bohemia,  Poland,  and 
Germany,  but  by  the  end  of  the  eighteenth  century  the  number  of  potash 
works  in  Hungary  had  decreased  because  of  deforestation  (69), 

Potash  in  Alum.  In  the  seventeenth  and  eighteenth  centuries,  chem 
ists  believed  that  potash  existed  only  in  the  vegetable  kingdom  Although 
it  had  been  shown  repeatedly  (by  Michael  Ettmuller,  G.  E  Stahl,  Jean 
Hellot,  Geoffroy  the  Younger,  and  J.  H.  Pott)  that  alum  can  be  made 
simply  by  treating  clay  with  sulfuric  acid,  chemists  did  not  suspect  thai 
the  vegetable  alkali  could  be  present  in  clay,  and  hence  did  not  recognize 
potash  as  an  essential  constituent  of  common  alum  (12,  15,  16,  17). 

In  an  undated  letter  to  J.  G,  Garni,  which  was  probably  written  in 
1774,  Scheele  stated  that  he  had  precipitated  alum  with  lime  water. 
"When  I  had  the  right  proportion  of  the  hme  water  to  the  acid  in  the 
alum,"  said  he,  "I  got  a  precipitate  of  alumina  and  gypsum  (calcium 
sulfate)  in  the  solution  .  .  .  and  I  found  neither  lime  or  gypsum  in 
the  clear  solution,  but  pure  water"  (IS).  Thus  it  is  evident  that  Scheele 
was  at  that  time  unaware  of  the  presence  of  potash  in  alum. 

When  A.  S.  Marggraf  tried  to  prepare  alum  from  alumina  and  vitriolic 
acid,  he  found  that  unless  he  added  fixed  alkali  he  obtained  no  crystals 
(19).  In  1777  Lavoisier  clearly  stated  that  potash  is  an  essential  con 
stituent  of  alum  (IS,  20).  In  analyzing  a  water  containing  aluminum 
sulfate,  which  the  younger  Cassini  had  sent  him  from  Italy,  Lavoisier 
added  some  potash  When  he  evaporated  the  solution,  he  obtained 
crystals  of  alum  and  realized  that  this  was  a  verification  of  the  results  of 
Marggraf  and  of  Macquer. 

"The  necessity  for  the  addition  of  a  portion  of  alkali  in  order  to 
form  alum  is  also  confirmed,"  said  Lavoisier,  "by  a  very  interesting  obser 
vation  of  M.  Monet  [A.-G.  Monnet  (1734-1817)]  on  the  earth  extracted 
from  the  alum  at  Tolfa;  the  chemical  examination  which  he  made  of 
specimens  of  this  earth,  brought  from  Italy  by  M.  Guettard,  showed  him 
that  it  contains  a  portion  of  fixed  vegetable  alkali  already  formed.  It 
is  doubtless  to  this  alkali  that  this  earth  owes  its  property  of  furnishing 


SOME  OLD  POTASSIUM  AND  SODIUM  COMPOUNDS  459 

alum  without  addition"  (20).  Since  Antoine-Grimoald  Monnet's  dis 
covery  of  potassium  in  the  alum  from  Tolfa  attracted  little  notice,  chem 
ists  still  continued  to  regard  that  element  as  peculiar  to  the  vegetable 
realm.  A.-F.  de  Fourcroy,  however,  was  aware  at  least  as  early  as  1789  of 
its  occasional  presence  in  minerals  (14). 

When  M,  H  Klaproth  analyzed  some  native  alum  (alunite)  from 
Cape  Miseno,  near  Naples,  he  computed  that  one  thousand  pounds  of 
it  contained  470  pounds  of  "alum  provided  by  Nature  herself  with  the 
requisite  quantity  of  pot-ash"  and  290  pounds  of  "alum  whose  crystalliza 
tion  is  promoted  by  adding  pot-ash"  (21).  The  presence  of  this  alkali 
raised  in  his  mind  the  question:  "As  this  grotto  consists  merely  of  volcanic 
tufa,  in  which  no  vegetation  takes  place,  whence  does  Nature  procure 
the  vegetable  alkali  requisite  to  the  generation  of  the  crystalhzable  alum?" 
(21). 

When  he  analyzed  some  native  saltpeter  from  the  Pulo  mine  at 
Molfetta  in  Apulia  and  found  that  "the  alkaline  base  of  prismatic  nitre 
constitutes  nearly  one-half  of  the  whole  of  that  compound,"  the  same 
question  struck  him  even  more  forcibly.  "The  conjecture  that  Nature 
possesses  means  of  producing  that  alkali  beyond  the  limits  of  the  vegetable 
kingdom,  nay,  even  without  any  immediate  influence  of  vegetation, 
acquires,  by  this  singular  phenomenon,  a  very  high  degree  of  probability" 
(21). 

Potash  in  Leucite,  In  1797  Klaproth  analyzed  some  Vesuvian  leucite, 
a  mineral  which  had  been  described  by  J.  J.  Ferber  in  1773,  and  found 
54.50  per  cent  of  silica,  24.50  per  cent  of  alumina,  and  nothing  else!  (22). 
In  order  to  account  for  the  21  per  cent  loss,  he  examined  the  mineral  more 
carefully,  and  was  astonished  to  find  potassium,  which  he  recognized  by 
the  crystalline  form  of  its  sulf ate  and  also  by  precipitating  it  witib.  tartaric 
acid  and  igniting  the  resulting  potassium  acid  tartrate  to  form  potassium 
carbonate,  which  "shot  into  prismatic  nitre"  when  he  treated  it  with  nitric 
acid.  He  also  analyzed  specimens  of  leucite  from  Albano,  Pompeii,  and 
Ronciglione,  and  concluded  that  "this  constituent  part  of  leucite,  which 
now  appears  in  the  character  of  an  oryctognostic  or  mineral  substance, 
is  no  other  than  pot-ash,  which  hitherto  has  been  thought  exclusively  to 
belong  to  the  vegetable  kingdom  ..."  (23).  When  the  American  min- 
eralogical  chemist  J.  Lawrence  Smith  analyzed  leucites  from  Vesuvius, 
Andernach,  Borghetta,  and  Frescati  in  1870,  he  also  found  rubidium  and 
cesium  in  every  specimen  he  tested  (24). 

Potash  in  Pumice.  In  1798  Dr.  Robert  Kennedy  of  Edinburgh  dem 
onstrated  the  presence  of  potash  in  pumice.  He  noticed  that  the  pumice 
fused  to  a  glassy  enamel.  Although  Klaproth  had  found  only  silica, 
alumina,  and  iron,  and  had  failed  to  detect  potash  in  the  specimen  he 


460  DISCOVERY  OF  THE  ELEMENTS 

analyzed,  he  mentioned  that  the  pumice  melted  in  the  porcelain  furnace 
in  Berlin.  Dr.  Kennedy  therefore  concluded  that  Klaproth's  specimen, 
as  well  as  his  own,  must  have  contained  some  alkali,  for  a  compound  of 
only  silica,  alumina,  and  a  very  little  iron  would  not  have  melted  at  this 
temperature  (25). 

A.-F.  de  Fourcroy  stated  in  1806  that  Klaproth  and  Vauquelin  had 
found  potash  "in  several  rocks,  especially  in  leucite,  feldspar,  and  some 
volcanic  products5'  (14). 

In  the  latter  half  of  the  nineteenth  century  the  United  States  was 
dependent  on  the  vast  Stassfurt  deposits  of  Germany  for  the  potassium 
compounds  needed  as  fertilizers.  In  1911  Congress  appropriated  funds 
for  a  search  for  domestic  minerals,  salts,  brines,  and  seaweeds  suitable 
for  potash  production  (67).  The  complex  brines  of  Searles  Lake,  Cali 
fornia,  a  rich  source  of  potassium  chloride,  have  been  worked  up  scien 
tifically  on  the  basis  of  phase-rule  studies  with  outstanding  success.  Oil 
drillers  exploring  the  Permian  Basin  for  oil  became  aware  of  the  possibility 
of  discovering  potash  deposits  through  chemical  analysis  of  the  cores  of 
saline  strata.  A  rich  bed  of  sylvinite,  a  natural  mixture  of  sylvite 
(potassium  chloride)  and  halite  (sodium  chloride),  was  found  at  Carls 
bad,  New  Mexico.  At  the  potash  plane  near  Wendover,  Utah,  the  raw 
material,  a  brine,  is  worked  up  by  solar  evaporation  (67). 

Potassium  in  Animals.  Professor  Abildgaard  of  Copenhagen  dis 
covered  potassium  in  the  blood  of  the  horse.  After  adding  nitric  acid  to 
the  blood,  he  prepared  and  purified  crystals  of  saltpeter  (26),  Potassium 
is  essential  to  both  plant  and  animal  life,  and  the  adult  human  body  con 
tains  more  potassium  than  sodium  (27). 

SOME  SODIUM  COMPOUNDS 

"Hence  with  diffusive  salt  old  Ocean  steeps 

His  emerald  shallows,  and  his  sapphire  deeps. 

Oft  in  wide  lakes,  around  their  warmer  brim 

In  hollow  pyramids  the  crystals  swim; 

Or,  fused  by  earth-born  -fires,  in  cubic  blocks 

Shoot  their  white  forms,  and  harden  into  rocks. 

Thus,  cavern  d  round  in  Cracow's  mighty  mines, 

With  crystal  walls  a  gorgeous  city  shines; 

Scoop'd  in  the  briny  rock  long  streets  extend 

Their  hoary  course,  and  glittering  domes  ascend  .  .  . 

Form'd  in  pellucid  salt  with  chissel  nice, 

The  pale  lamp  glimmering  through  the  sculptured  ice, 

With  wild  reverted  eyes  fair  Lotto*  stands, 

And  spreads  to  Heaven,  in  vain,  her  glassy  hands  ..."  (29) 

*  This  refers  to  3.  rock  salt  statue  of  Lot's  wife. 


SOME  OLD  POTASSIUM  AND  SODIUM  COMPOUNDS  461 

Salt,  The  oldest  Chinese  treatise  on  pharmacology  and  phanna- 
cognosy,  the  "Peng-Tzao-Kan-Mu,"  which  some  authorities  believe  to 
date  back  to  about  2700  B.C.,  describes  both  solar  and  rock  salt  Shu-Sha 
(or  Sou-Cha),  a  subject  of  the  Emperor  Huang,  invented  the  art  of 
extracting  salt  from  sea  water  (SO,  75),  In  about  300  B.C.,  Li-Ping, 
prefect  of  S-Tchuan  province,  discovered  salt  deposits  in  the  earth;  the 
inhabitants  had  obtained  their  salt  hitherto  from  Chan-Si  in  exchange 
for  tea.  L.  G.  M.  Baas-Becking  stated  that  the  early  Chinese  pictogram 
for  salt  was  undoubtedly  a  diagram  of  the  hopper-shaped  crystal  of 
sodium  chloride  and  is  probably  the  earliest  picture  of  a  crystal. 


From  Li  Ch'wo-p'ing's  "Chemical  Arts  of  Old  China" 

Pumping  Salt  brine  in  ancient  China,  from  a  depth  of  1200  feet  or  more. 
In  addition  the  Chinese  produced  lake  salt,  sea  salt,  and  rock  salt. 


An  account  of  the  salt  industry  at  Tzu-Liu-Ching  published  by  Li 
Jung  (ca.  1820-1889)  in  1890  was  translated  by  Lien-che  Tu  Fang  and 
published  with  handsome  illustrations  in  Isis  (65).  Along  the  seacoast 
from  Manchuria  to  Kwangtung,  salt  is  produced  by  evaporation  of  sea 
water.  In  the  northwest  it  is  obtained  by  evaporation  of  the  water  of 
salt  ponds  and  salt  lakes.  In  the  southwest  the  rock  salt  deposits  are 
reached  by  wells.  In  Szechwan  the  rock  salt  is  accompanied  at  some 


462  DISCOVERY  OF  THE  ELEMENTS 

places,  including  Tzu~liu-ching,  by  natural  gas,  which  is  burned  to  acceler 
ate  the  evaporation  (65). 

Two  bricks  or  tiles  bearing  reliefs  depicting  the  salt  industry  as 
practiced  in  the  first  or  second  century  A.D.  have  been  unearthed  in 
Szechwan.  Rubbings  of  these  bricks,  which  were  used  in  the  construction 
of  two  tombs  of  the  Later  Han  dynasty  (A.D.  24-220),  were  published 
in  IOT  by  Richard  C.  Rudolph  (66). 

The  prescriptions  in  the  Ebers  papyrus  (sixteenth  century  B.C.) 
mention  both  common  salt  and  soda  (natron)  (31).  Both  the  Old  and 
New  Testaments  abound  in  literal  and  figurative  allusions  to  salt:  "Ye 
are  the  salt  of  the  earth",  "Have  salt  in  yourselves  and  have  peace  one 
with  another"  (32).  Strabo  described  the  mining  of  rock  salt  and  its 
preparation  from  salt  springs  in  18  A.D.  (1).  Dioscorides  of  Anazarba 
said  in  64  A.D.  that  the  best  salt  came  from  Cyprus,  Sicily,  Africa,  and 

Phrygia  (I). 

Aboriginal  Indians  in  the  southern  part  of  what  is  now  the  United 
States  used  to  purify  salt  by  allowing  water  to  percolate  through  it  in 
leaching  baskets  (33)  and  boilmg  the  strained  leachings  down  over  a 
fire.  Hernando  de  Soto's  party  prepared  salt  by  this  old  Indian  method 
in  1541  for  their  expedition  through  Arkansas  (34).  The  Aztecs  con 
centrated  the  water  from  salt  lakes  by  boiling  it  down  in  pottery  vessels 
and  also  by  allowing  it  to  stand  in  shaUow  pools  where  the  sun  could 
evaporate  it.  They  used  it  not  only  as  a  condiment  but  also  for  preserving 

meat  (33). 

Herman  Boerhaave  stated  that  the  salt  mines  of  Wieliczka,  near 
Cracow,  Poland,  were  discovered  in  the  year  1251.  He  described  them 
as  "a  subterraneous  republic,  which  has  its  polity,  laws,  families,  and 
even  high-ways  and  common  carriers.  .  .  .  When  a  traveller  is  arrived 
at  the  bottom  of  this  strange  abyss,  ...  he  is  surpriz'd  with  a  long  series 
of  lofty  vaults  .  .  .  which  .  .  .  appear  by  the  light  of  flambeaux  .  .  ^ 
as  so  many  crystals  .  .  .  casting  a  lustre  which  the  eye  can  scarce  bear" 

(35). 

When  the  British  fisheries  lacked  an  adequate  supply  of  pure  salt, 
Dr.  William  Brownrigg  published  an  important  book  "On  the  Art  of 
Making  Common  Salt,"  which  was  condensed  by  Sir  William  Watson 
and  published  in  1848  in  the  Philosophical  Transactions  (36). 

Per  Kalm  found  in  1748-51  that  the  inhabitants  of  Quebec  were 
entirely  dependent  on  France  for  their  salt.  Because  of  a  French 
monopoly,  the  salt  industry  could  not  flourish  in  Quebec  (37) . 

The  salt  industry  of  Avranchin  was  mentioned  by  G.  Dumoulin  in 
1631  and  described  by  Jean-Etienne  Guettard  in  1758.  In  the  calm  bay, 
the  sea  water  deposited  its  salt  with  the  sand.  By  means  of  horse-drawn 
rakes,  the  salty  sand  was  collected  in  spiral-shaped  piles,  which  were  then 


SOME  OLD  POTASSIUM  AND  SODIUM  COMPOUNDS  463 

covered  with  twigs  and  clay.  The  leaching  with  sea  water  was  done  in 
wooden  boxes,  the  brine  filtering  through  the  sand  and  passing  through 
tubes  into  the  boiling-house.  The  evaporating  pans  were  of  lead,  and 
the  output  one  hundred  pounds  of  salt  per  day  (38). 

The  Medical  Repository  for  1802  stated  that  "at  Dennis,  in  the 
county  of  Barnstable  [Massachusetts],  common  salt  is  crystallized  from 
ocean  water,  without  culinary  heat  or  boiling,  in  considerable  quantity. 
The  amount  is  stated  at  20,000  bushels  a  year  of  domestic  sea  salt  This  is 
estimated  at  one-fifth  of  the  quantity  consumed  in  the  Cape  Cod  fishery 
annually"  (39). 


\ 


'^  \\vc\ 


From  Lt  Ch'wo-p'mg's  "Chemical  Arts  of  Old  China1' 

Ancient  China's  Lake  Salt  was  produced  in  plants  such  as  this,  usually  built 
along  the  shores  of  salt  lakes,  in  the  Kansu  and  Shansi  provinces. 


In  colonial  times,  some  salt  was  made  by  evaporating  sea  water  from 
large  boilers,  but  much  of  it  was  imported  from  the  West  Indies.  Timothy 
Dwight,  president  of  Yale  College,  in  his  "Travels  in  New  England  and 
New  York,"  described  its  manufacture  by  solar  evaporation  at  Yarmouth 
and  Dennis,  Massachusetts,  at  the  beginning  of  the  nineteenth  century. 
Four  kinds  of  shallow,  water-tight  wooden  vats  were  used.  "The  first 
class,  or  that  next  to  the  ocean,  is  called  the  water  room;  the  second  the 
pickle  room;  the  third  the  lime  room,  and  the  fourth  the  salt  room. 
Each  of  these  rooms,  except  the  first,  is  placed  so  much  lower  than 
the  preceding  that  the  water  flows  readily  from  it  into  another  in  the 
order  specified.  The  water  room  is  filled  from  the  ocean  by  a  pump, 


464  DISCOVERY  OF  THE  ELEMENTS 

furnished  with  vans  or  sails,  and  turned  by  the  wind,  Here  it  continues 
until  of  the  proper  strength  to  be  drawn  into  the  pickle  room,  and  thus 
successively  into  those  which  remain.  The  lime,  with  which  the  water 
of  die  ocean  abounds,  is  deposited  in  the  lime  room.  The  salt  is  formed 
into  small  crystals  in  the  salt  room,  very  white  and  pure,  and  weighs  from 
seventy  to  seventy-five  pounds  a  bushel.  The  process  is  carried  on  through 
the  warm  season.  After  the  salt  has  ceased  to  crystallize,  the  remaining 
water  is  suffered  to  freeze.  In  this  manner  a  large  quantity  of  Glauber's 
salt  is  obtained  in  crystals,  which  are  clean  and  good.  .  .  .  The  marine 
salt  made  here  is  sold  for  seventy-five  cents  a  bushel;  amd  the  Glauber's 
salt,  at  from  six  to  ten  cents  a  pound.  .  .  .  The  people  of  Dennis,  the 
town  immediately  East  of  Yarmouth,  began  this  business.  .  .  .  May  it 
not  be  believed  that  many  thousands  of  persons  may,  one  day,  be  profitably 
employed  in  making  salt  along  the  immense  extent  of  our  shore  .  .  . "  ( 40 ) . 

In  about  1865  Professor  B.  F.  Mudge,  first  president  of  the  Kansas 
Academy  of  Science,  gave  a  geological  description  of  the  salt  beds  of 
Kansas  in  the  Republican,  Solomon,  and  Saline  valleys.  This  enormous 
deposit  extends  from  northern  Kansas  into  Oklahoma  and  Texas  (41 ). 

The  United  States  has  inexhaustible  supplies  of  salt  (68,  70).  New 
York,  Ohio,  Michigan,  Kansas,  Louisiana,  and  Texas  all  have  vast  com 
mercial  deposits  of  solid  salt  (halite).  One  of  the  most  interesting  of 
these  salt  mines  is  situated  beneath  the  City  of  Detroit.  The  Ohio  Valley- 
Kanawha  area  and  the  Saginaw  Valley  of  Michigan  have  underground 
brines  which  yield  salt,  calcium  chloride,  magnesium  chloride,  and  bro 
mine.  The  hydraulic  mining  of  salt  in  Ohio  gave  Herman  Frasch  the  idea 
for  his  remarkable  process  of  mining  Louisiana  sulfur  by  melting  it  under 
ground  with  superheated  water  and  pumping  it  out  in  molten  form  ( 68 ) . 
Another  source  of  sodium  chloride  is  the  Great  Salt  Lake  in  Utah. 

Natural  Soda.  The  proverb  "As  he  that  taketh  away  a  garment  in 
cold  weather,  and  as  vinegar  upon  nitre,  so  is  he  that  singeth  songs 
to  an  heavy  heart"  (Prov.  25,  20)  is  an  allusion  to  the  action  of  vinegar 
on  sodium  carbonate.  The  detergent  property  of  this  alkali  is  mentioned 
in  Jeremiah  2,  22:  "For  though  thou  wash  thee  with  nitre  and  take  thee 
much  sope,  yet  thine  iniquity  is  marked  before  me." 

In  the  eighteenth  century  some  chemists  believed  that  the  word 
natrum  referred  to  saltpeter  (potassium  nitrate).  Geoffroy  the  Elder, 
however,  distinguished  clearly  between  the  niter,  or  natrum,  of  the 
ancients  (sodium  carbonate)  and  modern  niter  (saltpeter).  Even  in  his 
time,  the  inhabitants  of  Smyrna  and  Ephesus  still  washed  their  clothes 
with  a  lye  leached  from  small  alkaline  hillocks  in  their  fields,  "The 
ancient  nitre/3  said  Geoffroy,  "was  likewise  used  to  make  Glass,  being 
mixed  with  Sand;  as  they  afterwards  did  with  the  salt  of  the  Plant  Kali, 
or  Glass-Wort,  as  may  be  gathered  from  what  Tacitus  says  .  .  .  that 


SOME  OLD  POTASSIUM  AND  SODIUM  COMPOUNDS  465 

the  Sands  of  Palestine  and  Syria,  near  Egypt,  were  made  into  Glass  with 
Nitre*'  (42).  In  Geoffrey's  time  sodium  carbonate  was  rare  in  Europe, 
and  little  used. 

In  1799  Luigi  Palcani  published  analyses  of  two  authentic  specimens 
of  natural  Oriental  natrum:  one  which  Pietro  Andrea  Mattioli  had 
brought,  more  than  two  centuries  before,  from  Constantinople  for  Ulisse 
Aldrovandfs  Museum  of  Natural  History,  and  another  which  Edward 
Wortley  Montague  had  brought  from  Alexandria.  Palcani  found,  as  du 
Hamel  had  stated,  that  the  natrum  was  composed  mainly  of  sodium 
carbonate  (43).  It  also  contained  varying  amounts  of  sodium  bicarbon 
ate,  sodium  chloride,  sodium  sulfate,  and  water  (44). 

Another  early  description  of  the  African  trona  is  to  be  found  in  the 
first  volume  of  Crell's  Neueste  Entdeckungen  in  der  Chemie.  C.  Bagge, 
Swedish  consul  to  Tripoli,  said  that  a  very  thin  crust  of  white,  crystalline 
trona  covered  the  ground  at  a  place  two  days'  journey  from  Fezzan  in 
the  Sahara.  It  was  shipped  to  Egypt,  Tripoli,  and  "the  land  of  the 
Negroes"  to  be  used  in  bleaching  and  soap  making  (45).  The  Wadi 
Natrun,  or  Natron  Valley,  near  Cairo  and  Alexandria,  lies  below  the 
level  of  the  sea.  Its  lakes,  formed  by  the  flood  waters  of  the  Nile,  become 
almost  dry  in  summer,  and  its  great  deposits  of  natron  have  been  worked 
for  thousands  of  years  (46). 

Georg  Adolph  Suckow,  in  his  "Introduction  to  Economic  and  Techni 
cal  Chemistry,"  described  in  1784  the  preparation  of  soda  by  burning 
certain  marine  plants  such  as  Fucus  vesiculosus,  Chenopodium  maritimum, 
and  Salsola  kali,  and  leaching  it  from  the  half-vitrified  ashes.  This 
industry  flourished  at  Alicante,  Spain,  at  Alexandria,  Egypt,  and  along 
the  coasts  of  Italy  and  France  (47). 

When  these  natural  sources  of  soda  became  depleted  and  inadequate 
to  meet  the  demand,  various  processes  were  devised  for  the  manufacture 
of  it  from  the  cheapest  raw  material,  common  salt.  An  account  of  the 
most  successful  of  these  early  processes  and  the  tragic  story  of  its  dis 
coverer,  Nicolas  Leblanc,  has  been  told  by  Dr.  Ralph  E,  Oesper  in  the 
Journal  of  Chemical  Education  (71).  The  same  journal  also  contains 
other  valuable  articles  on  the  alkali  industry  by  Dr.  Oesper  (72),  E.  Berl 
(75),  and  Desmond  Reilly  (74). 

Glass.  Pliny  the  Elder  (in  Book  36,  Chapter  26  of  his  "Historia 
Naturalis")  described  a  pure  sand  found  on  the  Phoenician  coast  at  the 
mouth  of  the  river  Belus,  near  the  settlement  of  Ptolemais.  "The  shore," 
said  Pliny,  "does  not  exceed  half  a  mile  in  extent,  and  yet,  for  long  ages, 
it  was  the  only  source  of  sand  for  making  glass.  The  story  is  that  mer 
chants  put  in  there  with  a  cargo  of  crude  soda  (nitrum),  and  when, 
scattered  over  the  beach,  they  were  preparing  a  meal  and  could  find 
no  stones  of  the  right  height  to  prop  up  their  pots,  they  supported  them  on 


466  DISCOVERY  OF  THE  ELEMENTS 

lumps  of  soda  which  they  had  fetched  from  the  ship.  When  these  were 
melted  by  the  heat  and  mingled  with  the  sand,  transparent  streams  of  a 
strange  liquid  were  seen  to  flow,  and  thus  glass  was  discovered"  (48). 

Cornelius  Tacitus,  a  friend  of  Pliny  the  Younger,  also  mentioned  the 
manufacture  of  glass  by  fusing  native  niter  with  sand  from  the  beach  at 
the  mouth  of  the  river  Belus  (49), 

Although  pure  silica  and  pure  sodium  carbonate  would  yield  only 
soluble  "water  glass,"  K.  C.  Bailey  and  A.  Lucas  believe  that  if  the 
materials  used  by  the  Phoenicians  contained  lime  as  an  impurity,  true 
glass  could  possibly  have  been  produced  by  the  method  described  by 
Pliny  (44).  Many  writers,  however,  regard  Pliny's  account  as  highly 

improbable. 

The  composition  of  the  glass  found  in  the  tomb  of  Tut-ankh-Amen5 
according  to  Lucas,  suggests  that  it  may  have  been  made  by  fusing  to 
gether  a  mixture  of  natron  and  siliceous  sand  containing  calcium  carbonate 
as  an  impurity  (50).  The  Egyptians,  according  to  Albert  Neuburger, 
manufactured  glass  long  before  the  Phoenicians.  The  oldest  known 
piece  of  glass  is  in  the  Berlin  Museum.  It  is  a  green  bead  taken  from 
a  prehistoric  Egyptian  grave  believed  to  be  about  fifty-four  centuries 

old  (51), 

Herman  Boerhaave  once  wrote  with  deep  feeling:  "If  there  is  an 
art  useful  to  mankind,  it  is  certainly  that  of  making  glass.  Glass,  when 
ground,  corrects  the  defects  of  our  vision;  without  it,  as  soon  as  one  had 
reached  a  certain  age,  he  could  no  longer  hope  to  read"  (64). 

Glauber's  Salt.  When  Johann  Rudolph  Glauber  (1604-1670)  was 
visiting  Austria  in  his  youth,  he  was  stricken  with  a  serious  stomach 
ailment  which  was  finally  relieved  when  he  drank  water  from  a  spring 
near  Wiener-Neustadt.  When  he  evaporated  some  of  this  water,  he 
found  that  the  residue  contained  a  salt  'which  Paracelsus  called  enixum 
and  I  call  mirabile"  (52,  53).  Since  Glauber  succeeded  in  preparing  it 
from  common  salt,  made  an  extended  study  of  its  properties,  and  intro 
duced  its  use  into  medicine,  it  came  to  be  known  as  the  sal  mirabile  of 
Glauber  and  finally  as  Glaubers  salt,  sodium  sulfate  (54,  55,  56).  Al 
though  he  made  some  extravagant  claims  for  it,  Glauber  was  nevertheless 
conservative  enough  not  to  regard  it  as  the  elixir  of  life.  "But  let  no 
one  imagine,"  said  he,  "that  I  would  like  to  demonstrate  immortality  with 
it.  Alas,  no,  because  for  death,  no  herb  is  grown"  (52). 

Glauber's  salt  of  excellent  quality  was  manufactured  at  Dennis, 
Massachusetts.  At  the  beginning  of  the  nineteenth  century,  about  fifty 
tons  per  year  were  produced  there  (39 ) . 

Sodium  in  Basalt  and  Lava.  Nicholsons  Journal  for  October,  1798, 
contains  an  account  of  the  first  discovery  of  sodium  in  a  stony  mineral. 
Early  in  August  of  that  year  Dr.  Robert  Kennedy  announced  to  the  Royal 


SOME  OLD  POTASSIUM  AND  SODIUM  COMPOUNDS  467 

Society  of  Edinburgh  that  he  had  discovered  soda  in  several  varieties 
of  Scottish  whinstone  and  in  lava  from  Mt,  Aetna  (25).  He  used  the 
term  "whinstone"  to  include  basalt,  trap,  and  certain  kinds  of  porphyry, 
wacke,  and  other  argillaceous  stones.  When  he  analyzed  a  specimen 
which  had  been  broken  from  one  of  the  famous  basaltic  columns  of 
Staffa,  he  found  that  the  sum  of  the  earths,  silica,  and  iron  never 
amounted  to  more  than  94  per  cent.  Suspecting  the  presence  of  an 
alkali,  he  heated  the  pulverized  mineral  with  pure  sulfuric  acid  and 
extracted  a  salt  which  he  identified  as  sodium  sulfate  (25).  He  proved, 
moreover,  that  the  sodium  compounds  had  not  been  dissolved  from  his 
glass  apparatus.  Dr.  Kennedy  also  found  4  per  cent  of  soda  in  a  speci 
men  of  lava  brought  to  him  by  Sir  James  Hall  and  Dr.  James  Home  from 
the  famous  current  of  Mt.  Aetna  which  in  1669  had  destroyed  part  of 
the  town  of  Catania.  He  published  these  analyses  in  1800  in  Nicholsons 
Journal  (25). 

"The  celebrated  Mr.  Klaproth  of  Berlin,"  said  Dr.  Kennedy,  "has 
already  shown  that  pot-ash  enters  into  the  composition  of  several  stony 
substances,  and  by  the  experiments  described  in  this  paper,  the  other 
fixed  alkali,  soda,  has  also  been  proved  to  exist  in  mineral  bodies,  as  it 
has  been  separated  from  nine  different  varieties  .  .  ."  (25). 

Richard  Kirwan  mentioned  "the  ingenious,  accurate,  and  skilfully 
conducted  analyses  of  Dr.  Kennedy,  who  bids  fair  to  rival  the  excellence 
attained  by  the  greatest  masters  of  that  sublime  and  difficult  art"  (57). 

Klaproth  showed  in  1800  that  cryolite,  a  mineral  discovered  a  few 
years  previously  in  Greenland,  also  contains  sodium  (58). 

Sodium  in  Plants  and  Animals.  By  macerating  certain  plants  in 
warm  water  acidified  with  different  mineral  acids,  G.-F.  Rouelle  (1703— 
1770 )  prepared  and  identified  the  neutral  sodium  salts  of  the  correspond 
ing  acids  and  thus  demonstrated  the  presence  of  the  mineral  alkali 
( sodium  carbonate)  in  these  plants.  He  believed  that  the  sodium  carbon 
ate  was  not  merely  absorbed  from  the  soil  but  that  it  was  a  true  product 
of  vegetation  (II). 

Although  sodium  is  not  essential  to  plant  life,  plants  grown  under 
natural  conditions  do  absorb  sodium  compounds  from  the  soil.  As  early 
as  1874,  G.  Bunge  pointed  out  that,  in  experimental  attempts  to  raise 
plants  entirely  free  from  sodium,  glass  containers  must  be  avoided  be 
cause  of  the  solubility  of  sodium  compounds  contained  in  the  glass  ( 59 ) . 
In  1878  Pierre-Paul  Deherain  raised  beans  and  potatoes  in  an  artificial 
culture  medium  entirely  free  from  sodium  (60,  61). 

Hilaire-Marin  Rouelle,  a  younger  brother  of  Guillairme-Fran^ois 
(Rouelle  the  Elder),  observed  in  1773  that  the  blood  of  man  and  animals 
contains  free  mineral  alkali,  common  salt,  and  potassium  chloride 
("sylvisches  Fiebersalz")  (26,  62).  Jean-Baptiste-Michel  Bicquet  made 


468  DISCOVERY  OF  THE  ELEMENTS 


this  discovery  independently  at  about  the  same  time  (63).  Sodium 
occurs  in  all  animal  organs,  principally  as  sodium  chloride,  but  also  as 
secondary  sodium  orthophosphate,  sodium  sulfate,  sodium  carbonate, 
sodium  hydrogen  carbonate,  and  other  compounds.  Together  with 
potassium,  it  is  essential  for  animal  life  (27,  60). 


LITERATURE  CITED 

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(6)  O'CONNOR,  A.   CONDORCET,  "Oeuvres  de  Condorcet,"  Vol.  2,  Firmm  Didot 

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(7)  BOERHAAVE,   H,   "Elemens  de   chymie,"   Vol.   5,   Chardon,   fils,   Paris,    1754, 

pp.  263-4 

(8)  BLACK,  JOSEPH,   "Experiments  upon   Magnesia  Alba,   Quicklime,    and   Other 

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(JO)     NORDENSKIOLD,  A   E.,  "C    W    Scheele.  Efterlemnade  bref  och  anteckningar," 
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Sir  Humphry  Davy,  1778-1829.  English  chemist 
and  physicist.  One  of  the  founders  of  electrochemis 
try.  Inventor  of  the  safety  lamp  for  miners.  He 
was  the  first  to  isolate  potassium,  sodium,  calcium, 
barium,  strontium,  and  magnesium.  Davy  in  Eng 
land  and  Gay-Lussac  and  Thenard  in  France,  -work 
ing  independently,  were  the  first  to  isolate  boron. 


There  is  now  'be-fore  us  a  boundless  prospect  of  novelty 
in  science;  a  country  unexplored,  but  noble  and  fertile 
in  aspect;  a  land  of  promise  in  philosophy  (1). 


18 

Three  alkali  metals 


A  number  of  the  chemical  elements,  including  some  that  play  an 
important  role  in  modern  life,  remained  practically  unknown  out 
side  the  scientific  world  for  many  years  after  their  discovery 
Borne,  like  tellurium,  vanadium,  and  titanium,  were  forgotten  for 
several  decades  even  by  chemists,  and  were  later  rediscovered. 
The  reader  will  recall,  however,  that  when  phosphorus  was  dis 
covered  in  the  latter  half  of  the  seventeenth  century  the  news 
spread  rapidly  throughout  Europe.  In  a  similar  manner  Davys 
isolation  of  sodium  and  potassium  immediately  fired  the  imagi 
nation  of  the  nineteenth-century  public  and  aroused  intense  in 
terest.  These  elements,  like  phosphorus,  made  their  entrance 
upon  the  chemical  stage  in  a  manner  nothing  short  of  dramatic, 
and  the  accompanying  phenomenon  of  light  helped  to  focus  all 
eyes  upon  them.  Lithium,  however,  entered  the  chemical  world 
in  a  more  a  met  manner  and  uos  introduced  by  a  scientist  of 
lesser  prominence,  ].  A.  Arfwedson,  a  student  of  Berzelius. 


POTASSIUM  AND  SODIUM 


A 


.ncient  writers  did  not  distinguish  between  sodium  carbonate 
(the  mineral  alkali)  and  potassium  carbonate  (the  vegetable  alkali)  (42}. 
When  Johann  Bohn  prepaied  aqua  regia  in  1683  by  distilling  a  mixture  of 
salt  and  aqua  fortis  (nitric  acid),  he  noticed  that  the  cubic  crystals  which 
remained  differed  from  those  of  saltpeter  prepared  in  the  ordinary  manner 
from  wood  ashes.  This  clear  distinction  between  "cubic  saltpeter" 
(sodium  nitrate)  and  ordinary  saltpeter  was  an  important  step  in  the 
proof  that  soda  and  potash  are  two  different  alkalies.  In  the  latter 
part  of  the  eighteenth  century,  Torbern  Bergman  wrote:  "There  are  to 
this  day  persons  who  insist  that  the  vegetable  alkali  cannot  be  exhibited 
in  the  form  of  crystals,  notwithstanding  that  Professor  Bohnius  (Di$s, 
Physico  Chym.,  ann.  1696,  pa.  381)  of  Leipsic,  so  long  ago  as  the  end 
of  the  last  century,  had  demonstrated  the  contrary;  but  his  method  had 
been  so  long  unknown  that  it  was  lately  offered  to  the  public  as  a  new 
discovery"  (42,43,  44). 

473 


474 


DISCOVERY  OF  THE  ELEMENTS 


In  speaking  of  the  loss  to  both  chemistry  and  medicine  by  too 
narrow  specialization  in  either  science,  Herman  Boerhaave  once  wrote, 
"What  praise  then  is  not  merited  by  Jean  Bohn  and  Frederic  Hoffmann, 
who  excel  in  both  and  who  thereby  acquired  such  a  great  reputation" 

(45). 

Potash  was  made  on  a  small  scale  in  New  England  in  the  seventeenth 
century,  and  for  two  centuries  American  potash  and  pearlash,  made  by 
burning  wood  and  leaching  the  ashes,  were  shipped  to  European  coun 
tries,  with  incalculable  loss  to  American  agriculture  (50). 

Georg  Ernst  Stahl  distinguished  between  the  "natural  and  artificial 
alkalies"  (soda  and  potash)  as  early  as  1702,  and  noted  that  certain 


Henri-Louis  du  Hamel  ( or  Duhamel )  du 
Monceau,  1700-1782.  French  chemist 
and  agriculturist  who  proved  in  1736  that 
the  mineral  alkali  (soda)  is  a  constituent 
of  common  salt,  of  Glauber's  salt,  and  of 
borax  With  his  brother,  M.  de  Denarn- 
vilhers,  he  carried  out  important  experi 
ments  in  plant  nutrition  on  their  estate 


Gal   franc,  1823 
Drouais  pere  pinx ,  H.  Grcvedon  del 


sodium  salts  differ  in  crystalline  form  from  those  of  potassium  (42). 
Hermann  Kopp  quoted  a  passage  from  the  "Specimen  BecherianuirT  in 
which  Stahl  stated  that  the  natural  alkali  (soda)  in  common  salt  ap 
peared  in  the  retort  after  distillation  with  concentrated  oil  of  vitriol  or 
spirit  of  niter  (sulfuric  or  nitric  acid)  in  the  form  of  new  salts  differing 
from  the  corresponding  salts  of  the  artificial  alkali  (potash)  in  their 
crystalline  form,  solubility  in  water,  and  behavior  toward  heat. 

Henri-Louis  du  Harnel  du  Monceau  (or  Dumonceau)  proved  con 
clusively  in  1736  that  the  mineral  alkali  (soda)  is  a  constituent  of 
common  salt,  of  Glauber's  salt,  and  of  borax.  He  was  born  in  Paris  in 
1700  and  educated  at  Harcourt  College.  Even  before  his  election  to 


THREE  ALKALI  METALS  475 

membership,  the  Academy  of  Sciences  selected  him  to  study  a  disease 
which  was  threatening  the  saffron  crop  in  Gatinois.  Du  Hamel  found 
the  cause  of  it  to  be  a  parasitic  plant,  and  decided  to  devote  his  life 
to  scientific  agriculture  and  the  public  welfare  (50). 

Although  the  acidic  constituent  of  common  salt  was  already  known, 
the  nature  of  its  basic  constituent  was  still  a  matter  of  conjecture.  "Soda, 
natnim,  and  borax,"  wrote  du  Hamel  in  1736,  "give  with  vitriolic  acid 
Glauber's  salt,  with  acid  of  saltpeter,  cubic  saltpeter  [sodium  nitrate]; 
and  with  acid  of  salt,  a  kind  of  sea  salt.  Does  this  not  permit  one  to 
decide  as  to  the  base  of  the  sea  salt?"  (46). 

He  prepared  soda  from  salt  by  two  methods.  In  the  first  of  these, 
he  evaporated  a  mixture  of  salt  and  oil  of  vitriol,  heated  the  resulting 
Glauber's  salt  with  charcoal  dust  in  a  closed  crucible,  distilled  the  reduced 
mixture  with  wine  vinegar,  and  calcined  the  hard,  black  residue  of 
sodium  acetate  left  in  the  broken  retort.  In  his  other  method,  he  poured 
concentrated  spirit  of  saltpeter  (nitric  acid)  on  the  salt,  and  distilled 
off  the  resulting  aqua  regia.  After  repeating  the  distillation  four  times, 
he  exploded  the  residue  of  cubic  saltpeter  (sodium  nitrate)  with  charcoal 
dust  in  a  red-hot  crucible.  On  dissolving  the  residue,  he  obtained  "the 
crystalline  salt  of  an  alkali,  as  in  the  foregoing  process"  (46).  He  con 
cluded  that'  "soda  is  certainly  nothing  other  'than  the  true  base  of  sea 
salt;  this  is  shown  by  the  habitat  of  soda  plants"  (46). 

In  an  attempt  to  find  out  whether  the  presence  of  soda  or  potash 
depended  on  a  specific  difference  in  the  plants  which  produce  them  or 
on  the  composition  of  the  soils,  du  Hamel  devoted  many  years  to  agri 
cultural  experiments,  at  his  estate  at  Denainvilliers,  on  the  culture  of 
the  common  saltwort  (Salsola  kali),  a  plant  used  for  the  manufacture  of 
soda  ash.  The  final  analyses  of  the  ash  of  tiiis  plant  proved  that  in  the 
first  year  the  mineral  alkali  still  predominated,  but  that  in  succeeding 
years  the  vegetable  alkali  rapidly  increased  until  finally,  after  a  few 
generations,  the  soda  had  almost  disappeared  (SO).  In  these  experi 
ments,  he  had  for  many  "years  the  invaluable  and  enthusiastic  help  of 
his  brother,  M.  de  Denainvilliers.  In  his  eulogy  of  du  Hamel  in  the 
History  of  the  Academy  of  Sciences,  the  Marquis  de  Condorcet  gave  the 
following  characterizations  of  the  two  brothers: 

While  M.  du  Hamel  wrote  his  books,  consulted  with  scientists,  kept  up  a 
correspondence  with  the  most  enlightened  men  in  Europe,  engaged  in  new 
scientific  researches,  and  planned  his  experiments  and  observations,  M.  de 
Denainvilliers  carried  out,  in  his  retreat,  the  observations  and  experiments 
which  his  brother  had  entrusted  to  him,  always  unknown  and  content  to  be  so 
.  .  .  asking  no  other  recompense  than  the  pleasure  of  having  done  good.  To 
judge  M.  du  Hamel,  one  would  have  to  see  him  at  Denainvilliers,  the  fields 
covered  with  exotic  productions  which  were  enriching  growers  whose  fathers 


476        DISCOVERY  or  THE  ELEMENTS 

had  not  known  even  the  names  of  these  useful  and  salutary  plants,  .  .  .  forests 
filled  with  exotic  trees  bi ought  from  all  countries  of  the  globe,  .  .  all  the 
instruments  invented  for  observing  nature  and  studying  her  laws,  distributed 
in  the  mansions,  in  the  gardens,  in  the  parks;  and  in  the  midst  of  all  these  objects 
of  instruction,  two  men  united  by  the  love  of  the  good,  different  in  character 
as  in  occupation  .  .  .  (50). 

In  his  books,  M.  du  Hamel  reported  his  own  experiments  and  their 
results,  and  also  included  much  elementary  information  for  the  use  of 
practical  fanners.  "At  the  age  of  fifty  years,"  said  Condorcet,  "he  was 
one  of  the  best  informed  men  in  Europe  in  all  the  scientific  branches  with 
the  applications  of  which  he  later  occupied  himself  almost  exclusively 
.  .  .  and  if  he  has  often  been  justly  cited  to  show  what  use  scholars  ought 
to  make  of  their  learning,  one  can  also  prove  by  his  example  that,  in 
order  rightfully  to  aspire  to  the  honor  of  making  the  sciences  useful,  one 
must  be  very  learned"  (50).  M.  du  Hamel  "kept  all  his  life  the  prin 
ciples  of  religion  he  had  received  in  his  childhood;  ...  to  serve  humankind, 
to  penetrate  nature's  marvels,  and  to  ascribe  them  to  their  Author,  seemed 
to  him,  for  a  scientist  and  citizen,  the  most  fitting  exercise  of  piety"  (50). 
He  hved  tranquilly  with  his  nephews,  one  of  whom  shared  his  scientific 
labors.  After  the  death  of  M.  de  Denainvilliers,  these  nephews  and  a 
niece  relieved  M.  du  Hamel  of  aU  domestic  cares.  He  Hved  to  be  eighty- 
two  years  old. 

Georg  Brandt  m  1746  prepared  both  crystalline  and  amorphous 
sodium  carbonate  and  observed  that  the  latter  is  not  hygroscopic  and 
that  it  ciystallizes  more  readily  than  does  potassium  carbonate  (47). 

In  1758-59  A.  S.  Marggraf  prepared  very  pure  cubic  saltpeter  from 
common  salt.  "After  cooling  the  vessel  and  breaking  the  retort,"  said  he, 
"I  found  m  it  a  saline  substance  which  took  fire  on  glowing  charcoal, 
without  the  slightest  crackling  (just  as  ordinary  saltpeter  does  when  very 
pure)  and,  as  the  chemists  say,  detonated,  but  with  the  difference  that 
the  flame  was  yellow;  for  that  with  ordinary  prismatic  niter  is  usually 
whitish"  (48).  In  his  next  paper,  which  was  entitled  "Proof  that  the 
alkaline  part  separated  from  common  salt  is  a  true  alkaline  salt  and  not 
an  alkaline  earth,"  he  mentioned  the  yellow  flash  of  gunpowder  made  with 
cubic  saltpeter  and  the  blue  (violet)  flash  of  that  made  with  prismatic 
saltpeter  (48). 

Although  chemists  had  long  suspected  that  the  alkaline  earths  are 
metallic  oxides,  the  true  nature  of  soda  and  potash  was  not  surmised 
before  the  early  nineteenth  century  (28).  Lavoisier  believed  that  they 
might  contain  nitrogen: 

Up  to  the  present  [said  he]  the  principal  constituents  of  soda  are  no  better 
known  than  those  of  potash.  We  are  not  even  certain  whether  or  not  that 


THREE  ALKALI  METALS 


477 


substance  is  already  formed  in  vegetables  before  combustion.  Analogy  might 
lead  us  to  believe  that  nitrogen  is  one  of  the  principal  constituents  of  alkalies 
in  general,  and  we  have  the  proof  of  it  in  the  case  of  ammonia,  as  I  shall  explain; 
but  as  far  as  potash  and  soda  are  concerned,  we  have  only  slight  presumptions, 
not  yet  confirmed  by  any  decisive  experiment  (29). 


-*      3 


From  A  H  Norway's  "Highways  and  Bywa'js  in  Devon  and  CorniLall" 

St.  Michael's  mount  and  Bay  near  Penzances  Cornwall,  where  Sir  Humphry 

Davy  was  born 


In  his  list  of  elements  Lavoisier  mentioned  thirty- three  substances: 


light 

calonc 

oxygen 

nitrogen 

hydrogen 

sulfur 

phosphorus 

carbon 


muriatic  radical 
fluoric  radical 
boric  radical 
antimony 
silver 
arsenic 
bismuth 
cobalt 


copper 

tin 

iron 

manganese 

mercury 

molybdenum 

nickel 

gold 


platinum 

lead 

tungsten 

zinc 

lime 

magnesia 

baryta 

alumina 

silica 


In  commenting  on  this  list  he  said,  *1  have  not  included  in  this  table  the 
fixed  alkalies,  such  as  potash  and  soda,  because  these  substances  are 
evidently  compound,  although  however  the  nature  of  the  principles  which 
enter  into  their  composition  is  still  unknown"  (30).  The  chemical  nature 


478  DISCOVERY  OF  THE  ELEMENTS 

of  these  common  alkalies  remained  unknown  until  the  beginning  of  the 
nineteenth  century,  when  the  brilliant  young  English  chemist  Humphry 
Davy  succeeded  in  decomposing  both  of  them  with  his  voltaic  pile. 

High  above  an  azure  bay  on  the  rugged  coast  of  Cornwall  rises 
lofty  St.  Michael's  Mount,  a  gigantic  rock  surmounted  by  an  ancient 
turreted  castle.  The  nearby  town  of  Penzance  in  Mount's  Bay  may 
suggest  to  lovers  of  light  opera  the  adventurous  pirates  of  Gilbert  and 
Sullivan,  but  chemists  revere  it  as  the  birthplace  of  Sir  Humphry  Davy, 
who  once  gave  the  following  vivid  picture  of  the  scene  so  dear  to  him: 

The  sober  eve  with  purple  bright 
Sheds  o'er  the  hills  her  tranquil  light 
In  many  a  lingering  ray; 
The  radiance  trembles  on  the  deep, 
Where  rises  rough  thy  rugged  steep, 
Old  Michael,  -from  the  sea. 

Around  thy  base,  in  azure  pride, 

Flows  the  silver-crested  tide, 

In  gently  winding  waves; 

The  Zephyr  creeps  thy  cliffs  around,— 

Thy  cliffs,  with  whispering  ivy  crown  d,— 

And  murmurs  in  thy  caves  (2). 

Humphry  Davy  was  born  on  December  17,  1778.  He  was  a  healthy, 
active,  affectionate  child,  who  made  many  friends  by  his  knack  of  telling 
stories  and  reciting  original  verses,  His  teacher,  Dr.  Cardew,  said  the 
boy's  best  work  was  done  in  translating  the  classics  into  English  verse  (3). 
Davy's  schooling  ended  when  he  was  only  fifteen  years  old,  but  his  edu 
cation  continued  for  the  rest  of  his  life.  In  1795  he  was  apprenticed  to 
Bingham  Borlase,  a  surgeon  and  apothecary  in  Penzance,  and  two  years 
later  he  began  to  study  natural  philosophy  and  chemistry  (20).  His 
textbook  was  Lavoisier's  "Elements  of  Chemistry,"  his  reagents  were 
the  mineral  acids  and  the  alkalies,  and  his  apparatus  consisted  largely 
of  wine  glasses  and  tobacco  pipes.  When  he  was  twenty  years  old  Davy 
became  superintendent  of  the  Pneumatic  Institution  which  Dr.  Thomas 
Beddoes  had  recently  established  at  Clifton  for  studying  the  medicinal 
value  of  gases.  He  was  most  happy  in  sharing  the  delightful  home  life 
of  Dr.  Beddoes  and  the  social  contacts  with  such  distinguished  literary 
men  as  Robert  Southey  and  Samuel  Taylor  Coleridge  (4), 

In  1801  Count  Rumford  (Benjamin  Thompson)  obtained  for  Davy  a 
position  as  assistant  lecturer  on  chemistry  and  director  of  the  laboratory 
at  the  Royal  Institution.  In  the  Philosophical  Magazine  one  finds  the 
following  description  of  Davy's  first  lecture,  which  was  on  galvanism: 


THREE  ALKALI  METALS  479 

Sir  Joseph  Banks,  Count  Rumford  and  other  distinguished  philosophers 
were  present.  The  audience  was  highly  gratified,  and  testified  their  satisfac 
tion  by  general  applause.  Mr.  Davy>  who  appears  to  be  very  young,  acquitted 
himself  admirably  well.  From  the  sparkling  intelligence  of  his  eye,  his  ani 
mated  manner,  and  the  tout  ensemble,  we  have  no  doubt  of  his  attaining  dis 
tinguished  excellence  (5). 

Literary  persons  and  the  members  of  fashionable  society,  as  well  a: 
scientists,  flocked  to  his  lectures.  Davy  kept  a  careful  record  of  all  his 
experiments  and  showed  it  willingly  to  all  who  were  interested.  He 
remained  with  the  Royal  Institution  for  eleven  years,  and  then  retired  at 
the  time  of  his  marriage. 


Dr.      Thomas     Beddoes,     1760-1808. 

English  physician  and  chemist,  Foun 
der  of  the  Pneumatic  Institution  at 
Clifton  for  studying  the  therapeutic 
value  of  gases.  Sir  Humphry  Davy 
became  the  superintendent  of  this  in 
stitution  at  the  age  of  twenty  years 


Humphry  Davy's  greatest  successes  were  in  the  field  of  electro 
chemistry.  In  his  first  attempts  to  decompose  the  caustic  alkalies,  he 
used  saturated  aqueous  solutions,  but  succeeded  in  decomposing  nothing 
but  the  water.  On  October  6,  1807,  however,  he  changed  his  plan  of 
attack.  "The  presence  of  water  appearing  thus  to  prevent  any  decompo 
sition,"  said  he,  "I  used  potash  in  igneous  fusion"  (22S  23,  26). 

To  his  great  surprise  he  noticed  intense  light  at  the  negative  pole 
and  a  column  of  flame  rising  from  the  point  of  contact.  When  he  reversed 
the  current  the  flame  came  always  from  the  negative  pole.  Since  perfectly 
dry  potash  is  a  non-conductor,  Davy  gave  it  a  brief  exposure  to  the  air: 


480 


DISCOVEBY  OF  THE  ELEMENTS 


A  small  piece  of  potash  [said  he],  which  had  been  exposed  for  a  few  sec 
onds  to  the  atmosphere  so  as  to  give  conducting  power  to  the  surface,  was 
placed  upon  an  insulated  disc  of  platina,  connected  with  the  negative  side  of 
the  battery  of  the  power  of  250  of  6  and  4,  in  a  state  of  intense  activity;  and  a 
platina  wire,  communicating  with  the  positive  side,  was  brought  in  contact  with 
the  upper  surface  of  the  alkali.  The  whole  apparatus  was  in  the  open  atmos 
phere. 


Electrochemical  Apparatus  of 
Sir  Humphry  Davy.  Fig.  1 
Agate  cups.  Fig  2  Gold 
cones,  Fig.  3.  Glass  tubes 
Fig.  4  The  two  glass  tubes 
with  the  intermediate  vessel. 
In  all  the  figures,  AB  denote 
the  wires,  one  positive  and 
one  negative,  and  C  the  con 
necting  pieces  of  moistened 
amianthus. 


Under  these  circumstances  [said  DavyJ  a  vivid  action  was  soon  observed 
to  take  place.  The  potash  began  to  fuse  at  both  its  points  of  electrization.  There 
was  a  violent  effervescence  at  the  upper  surface;  at  the  lower,  or  negative,  sur 
face,  there  was  no  liberation  of  elastic  fluid;  but  small  globules  having  a  high 
metallic  lustre,  and  being  precisely  similar  in  visible  characters  to  quicksilver, 
appeared,  some  of  which  burnt  with  explosion  and  bright  flame,  as  soon  as  they 
were  formed,  and  others  remained,  and  were  merely  tarnished,  and  finally 
covered  by  a  white  film  which  formed  on  their  surfaces. 

These  globules,  numerous  experiments  soon  shewed  to  be  the  substance  I 
was  in  search  of,  and  a  peculiar  inflammable  principle  the  basis  of  potash.  1 
found  that  the  platina  was  in  no  way  connected  with  the  result,  except  as  the 


THREE  ALKALI  METALS 


481 


medium  for  exhibiting  the  electrical  powers  of  decomposition;  and  a  substance 
of  the  same  land  was  produced  when  pieces  of  copper,  silver,  gold,  plumbago, 
or  even  charcoal  were  employed  for  compleating  the  circuit. 

The  little  metallic  globules  always  appeared  at  the  cathode,  and 
these  had  an  astonishing  way  of  bursting  into  flame  when  thrown  into 
water.  They  skimmed  about  excitedly  with  a  hissing  sound,  and  soon 
burned  with  a  lovely  lavender  light  Davy  found  that  the  new  metal 


Apparatus  of  Sir  Humphry 
Davy.  Fig.  1.  Retort  of  plate 
glass  for  heating  potassium  in 
gases.  Fig  2.  Platinum  tray 
for  receiving  the  potassium 
Fig.  3.  Platinum  tube  for  re 
ceiving  the  tray  in  distillation 
experiments.  Fig,  4  Ap 
paratus  for  taking  the  vol 
taic  spark  in  sulfur  and 
phosphorus 


liberated  hydrogen  from  the  water  and  that  the  flame  was  caused  by  the 
burning  of  this  gas  (6,  23).  Because  he  had  obtained  the  metal  from 
potash,  he  named  it  potassium.  Dr.  John  Davy,  who  was  present  when 
potassium  was  isolated  for  the  first  time,  said  that  his  brother  became 
greatly  excited  and  almost  delirious  with  joy  (7, 19) . 

In  1811  the  Irish- American  chemist  William  James  MacNeven  pub 
lished  in  the  American  Philosophical  and  Medical  Register  an  article  on 
the  decomposition  of  potash  in  which  he  described  the  preparation  of 


482  DISCOVERY  OF  THE  ELEMENTS 

potassium  metal  by  reduction  of  potash  with  iron  turnings  in  a  sealed 
gun  barrel  (71). 

After  his  successful  decomposition  of  caustic  potash  Humphry  Davy 
attempted  to  decompose  caustic  soda  by  a  similar  method,  and  found  that 
a  larger  current  was  required  (6),  or,  as  he  himself  expressed  it,  that 
"the  decomposition  demanded  greater  intensity  of  action  in  the  batteries, 
or  the  alkali  was  required  to  be  in  much  thinner  and  smaller  pieces": 

With  the  battery  of  100  of  6  inches  in  full  activity  [he  explained]  I  obtained 
good  results  from  pieces  of  potash  weighing  from  40  to  70  grains,  and  of  a 
thickness  which  made  the  distance  of  the  electrified  metallic  surfaces  nearly 
a  quarter  of  an  inch;  but  with  a  similar  power  it  was  impossible  to  produce  the 
effects  of  decomposition  on  pieces  of  soda  of  more  than  15  or  20  grains  in 
weight,  and  that  only  when  the  distance  between  the  wires  was  about  one- 
eighth  or  one-tenth  of  an  inch.  The  substance  produced  from  potash  remained 
fluid  at  the  temperature  of  the  atmosphere  at  the  time  of  its  production;  that 
from  soda,  which  was  fluid  in  the  degree  of  heat  of  the  alkali  during  its  forma 
tion,  became  solid  on  cooling,  and  appeared  having  the  lustre  of  silver  (23,  24) , 
Thus  only  a  few  days  after  the  discovery  of  potassium  Davy  was  able  to 
announce  the  isolation  of  another  new  metal,  which  he  named  sodium. 

In  the  following  month  the  Quaker  chemist  William  Allen  wrote  in 
his  diary:  "Eleventh  Month  16th.-Went  to  the  Royal  Institution  to  see 
Davy.— Pepys  went  with  me.  He  showed  us  his  new  experiments  on  the 
decomposition  of  potash  and  soda.  From  the  oxygen,  or  zinc  end  of  a 
combination  of  troughs,  pure  potash  was  decomposed,  oxygen  driven 
off,  and  a  new  substance  produced,  in  little  globules,  which  has  the 
properties  of  a  metal,  except  that  its  specific  gravity  is  only  sixteen, 
or  thereabouts.  The  globule  explodes  and  ignites  in  contact  with  water, 
and,  absorbing  oxygen  from  it,  returns  to  the  state  of  alkali.  One  part 
of  this  new  substance  amalgamates  with,  and  fixes,  forty-eight  parts  of 
quicksilver.  Pepys  and  I  concluded  we  would  cheerfully  have  walked 
fifty  miles  to  see  the  experiment.  Here  is  another  grand  discovery  in 
chemistry"  (72). 

However,  it  still  remained  for  Davy  to  prove  the  elementary  nature 
of  these  metals,  which  many  chemists  believed  to  be  compounds  of  the 
alkali  and  hydrogen.  Gay-Lussac  and  Thenard  argued,  for  example,  that, 
since  ammonium  =  ammonia  +  hydrogen,  potassium  =  potash  + 
hydrogen.  It  was  finally  proved,  however,  that  no  hydrogen  can  be 
evolved  from  potassium,  and  that  Davy  was  correct  in  regarding  sodium 
and  potassium  as  elements  (8). 

Mr.  A.  Combes,  one  of  Davy's  admirers,  communicated  some  inter 
esting  comments  on  this  discovery  to  Nicholsons  Journal  (27): 

I  attended  his  course  of  lectures  of  1807  [said  Mr.  Combes]  and  in  refer 
ring  to  my  notes  I  find  that  he  stated  it  as  a  fact,  that  all  bodies  of  known  com- 


TH&EE  ALKALI  METALS          483 


Edgar  F«7i5  Smith  Memorial  Collection,,  University  of  Pennsylvania 

A  Letter  by  Sir  Humphry  Davy  in  which  he  introduces   Mrne.  Lavoisier  de 

Rumford  to  Dr,  Ure  of  Glasgow. 


position  attracted  by  the  negative  pole  in  the  Voltaic  circuit  consisted  principally 
of  inflammable  matter,  and  were  naturally  positive;  and  that  it  was  probable 
therefore,  that  all  bodies  of  unknown  composition  attracted  by  this  pole,  and 
which  were  naturally  positive,  might  also  contain  inflammable  matter.  In  his 
lectures  in  1801,*  he  stated,  that,  in  looking  for  inflammable  matter  after  those 
ideas  in  the  fixed  alkalies,  he  had  discovered  it,  and  that  he  had  likewise  found 
what  he  had  not  expected,  that  it  was  metallic  in  its  nature.  In  this  instance 
sagacious  conjecture  and  sound  analogy  were  followed  up  by  experimental 
research,  and  ended  in  a  great  discovery. 

*  This  date  as  given  in  Nicholsons  Journal  is  obviously  incorrect. 


484 


DISCOVERY  OF  THE  ELEMENTS 


Davy's  isolation  of  the  alkali  metals  was  brilliant  in  every  sense  of 
the  word.  It  soon  led  to  the  discovery  of  the  alkaline  earth  metals  by 
a  similar  electrochemical  method,  and  the  alkali  metals  themselves  were 
destined  to  become  powerful  tools  in  the  search  for  other  elements. 

LITHIUM* 

At  the  close  of  the  eighteenth  century,  the  great  Brazilian  scientist 
and  statesman  Joze*  Bonifacio  de  Andrada  e  Silva  made  a  mineralogical 
journey  through  Scandinavia  (41).  He  was  born  on  June  13,  1763,  at 
Vila  de  Santos  near  Rio  de  Janeiro,  the  eldest  of  three  gifted  brothers, 
all  of  whom  were  sent  to  the  University  of  Coimbra,  Portugal,  to  complete 
their  education. 


Joze*  Bonifacio  de  Andrada  E  Silva, 
1763-1838.  Brazilian  scientist,  statesman 
and  poet  Discoverer  of  petalite  and 
spodumene,  mineials  in  which  Arfwedson 
discovered  lithium  He  worked  tirelessly 
to  improve  the  social  conditions  of  the 
dispossessed  Indians  and  enslaved  Ne 
groes  and  to  bring  about  their  gradual 
emancipation. 


,  Gal    dos  Braztleiros  Ilhis  ,  186 
A    Sisson,  hth 


On  recommendation  of  the  Duke  of  Lafoes,  Joz£  Bonifdcio  was 
elected  to  the  Academy  of  Sciences  and  in  1790  was  sent  on  a  journey 
through  France,  Germany,  the  Netherlands,  Scandinavia,  Bohemia, 
Hungary,  Turkey,  and  Italy  to  study  under  A.-L  Lavoisier,  A.-F.  de 
Fourcroy,  Laurent  Jussieu,  the  Abbe  R.-J.  Haiiy,  A.  G.  Werner,  and 
Alessandro  Volta.  In  1800  he  returned  to  Coimbra  to  teacli  metallurgy 
(51,  52,  53).  In  a  letter  to  Mine  Surveyor  Beyer  of  Schneeberg,  which 

*  See  also  Chapter  19,  pp,  494-502, 


THREE  ALKALI  METALS  485 

was  published  in  January,  1800  in  Scherers  Journal,  de  Andrada  de 
scribed  an  infusible,  laminated  mineral  from  Uto,  Sala,  and  the  Fmn- 
gruva  near  New  Koppaibeig,  which  he  called  petahte  and  which  dis 
solved  in  nitric  acid  veiy  slowly  and  without  effervescence,  and  another 
new  mineral  which  he  called  spodumene  (34). 

After  returning  to  Brazil  in  1819,  de  Andrada  became  Minister  of 
State  and  was  a  signer  of  the  Brazilian  constitution.  Like  many  a 
great  scientist  of  today,  he  was  obliged  to  live  for  several  years  in  exile, 
but  these  were  spent  in  quiet  study  in  France.  When  he  again  returned 
to  Brazil,  the  abdicating  Emperor  Dom  Pedro  1  confided  to  him  the  care 
and  education  of  the  royal  heirs.  De  Andrada  spent  the  closing  years  of 
his  life  in  retirement  on  an  island  in  the  Bay  of  Bio  de  Janeiro  and  died 
at  Niteroi  (Nictheroy)  on  April  6,  1838  (51,  52,  54). 

He  was  a  versatile  scientist  and  linguist,  a  gifted  poet,  and  a  great 
statesman  and  humanitarian  sincerely  devoted  to  the  best  interests  of 
his  fellow  countrymen  He  worked  tirelessly  to  improve  the  social  con 
ditions  of  the  dispossessed  Indians  and  the  -slaves  and  bring  about  their 
gradual  emancipation.  He  was  a  positivist,  or  disciple  of  Auguste  Comte? 
and  is  known  to  Brazilians  as  "the  father  of  independence"  (41).  A  fin$ 
biography  of  him  was  published  in  1938  by  a  Brazilian  author,  Venancio 
de  Figueiredo  Neiva  (41). 

Mineialogists  long  remained  in  doubt  as  to  the  existence  of  petalite 
until  E.  T.  Svedenstjerna  rediscovered  it  in  1817  on  Uto  (an  island  In 
Sweden),  thus  confirming  the  original  discovery  by  de  Andrada  (36). 

N.-L.  Vauquelin's  analysis  of  spodumene,  which  the  Abbe  Haiiy 
published  in  his  "Traite  de  Mineralogie"  in  1801,  showed  a  loss  of  9.5  per 
cent,  which  was  never  correctly  interpreted  until  J.  A.  Arfwedson  in 
1818  discovered  a  new  alkali  metal,  hthiurn,  first  in  petalite,  and  soon 
after  in  spodumene  and  in  lepidohte  (35).  Even  before  the  discovery 
of  lithium,  Johann  Nepomuk  von  Fuchs  observed  the  red  color  which 
spodumene  imparts  to  the  flame,  he  afterward  expressed  chagrin  because 
he  had  neglected  to  investigate  the  cause  of  this  color  (36).  Vauquelin 
detected  the  presence  of  an  alkali  in  a  specimen  of  petalite  obtained 
from  the  metallurgist  E.  T.  Svedenstjerna,  but  mistook  it  for  potash  (13, 
37),  Wilhelm  Hisinger  also  analyzed  this  mineral  at  least  as  early  as 
January,  1818,  and  obtained  preliminary  results  similar  to  those  of  Arf 
wedson  (38).  When  the  Reverend  Edward  Daniel  Clarke  of  the  Uni 
versity  of  Cambridge  analyzed  a  specimen  of  it  in  the  same  year,  his 
results  showed  a  puzzling  'loss"  of  1.75  per  cent,  the  reason  for  which 
became  evident  as  soon  as  Arfwedson's  analysis  was  published  (39,  40). 

Johan  August  Arfwedson,  the  discoverer  of  lithium,  was  born  at 
Skagerholms-Bruk,  Skaraborgs  Lan,  on  January  12,  1792  (10).  He 
studied  chemistry  under  Berzelius,  and  it  was  in  the  latter's  famous 


486 


DISCOVERY  OF  THE  ELEMENTS 


Stockholm  laboratory  that  he  made  this  great  discovery  at  the  age  of 
twenty-five  years.  Berzelius  described  this  chemical  event  in  a  letter 
to  C.-L.  Berthollet  written  on  February  9,  1818: 

The  new  alkali  [said  he]  was  discovered  by  Mr.  Arfvedson,  a  very  skillful 
young  chemist  who  has  been  working  in  my  laboratory  for  a  year  He  found 
this  alkah  in  a  rock  previously  discovered  by  Mr.  d'Andrada  in  the  mine  at  Uto 
and  named  by  him  petalite.  This  rock  consists  in  round  numbers,  of  80% 
silica,  17%  alumina,  and  3%  of  the  new  alkali.  To  extract  the  latter  from  it 
one  uses  the  ordinary  method  of  heating  the  pulverized  rock  with  barium  car 
bonate  and  separating  from  it  all  the  earths,  .  .  . 

This  alkali  [continued  Berzelius]  has  a  greater  capacity  for  saturating  acids 
than  the  other  fixed  alkalies,  and  even  surpasses  magnesia.  It  is  by  this  cir- 


Edward      Daniel     Clarke,      1769-1822. 

English  mineralogist  and  traveler  One 
of  the  founders  of  the  Cambridge  Philo 
sophical  Society.  One  of  the  first  chem 
ists  to  analyze  the  lithium  mineral 
petalite.  His  "Travels  in  Various  ^Coun 
tries  of  Europe,  Asia,  and  Africa"  con 
tains  intimate  glimpses  of  many  con 
temporary  scientists  and  their  labora 
tories.  See  ref.  (49). 


Engraved  by  W.  T.  Fry  from  an  original  picture 
by  J   Opie,  R  A 


cumstance  that  it  was  discovered.  For  the-  salt  with  the  [new]  alkali  as  base 
obtained  by  analysis,  exceeds  greatly  in  weight  what  it  ought  to  have  weighed 
if  its  base  had  been  soda  or  potash.  It  was  very  natural  to  conclude  that  a  salt 
with  an  alkali  base  which  is  not  precipitated  at  all  by  tartaric  acid  ought  to 
contain  soda.  So  did  Arfvedson  at  first,  but,  having  repeated  the  analysis  oi 
the  petalite  three  times  with  exactly  the  same  results,  he  thought  he  ought  to 
examine  each  constituent  more  thoroughly,  and  it  is  in  consequence  of  such  an 
examination  that  he  noticed  that  the  alkaline  substance  had  properties  different 
from  other  alkalies.  We  have  given  this  alkali  the  name  of  litbion  [lithia]  to 
recall  that  it  was  discovered  in  the  mineral  kingdom,  whereas  the  two  others 
were  [discovered]  in  the  vegetable  kingdom  (II) . 

Arfwedson  s  own  account  of  his  analysis  of  petalite  is  to  be  found 


THREE  ALKALI  METALS  487 

in  the  Annales  de  Chimie  et  de  Physique  for  1819.  He  found  that  it 
contained  silica,  alumina,  and  an  alkali  metal  which  he  tried  to  determine 
by  weighing  it  as  the  sulfate. 

But  [said  he]  it  was  still  necessary  to  learn  the  hase  of  the  salt.  Its  solu- 
tion could  not  be  precipitated  either  by  tartaric  acid  in  excess  or  by  platinum 
chloride.  Consequently  it  could  not  be  potassium.  I  mixed  another  portion  of 
a  solution  of  the  same  salt  with  a  few  drops  of  pure  potash,  but  without  its 
becoming  cloudy.  Therefore  it  contained  no  more  magnesia:  hence  it  must  be 
a  salt  with  soda  for  a  base.  I  calculated  the  quantity  of  soda  which  would  be 
necessary  to  form  it;  but  it  always  resulted  in  an  excess  of  about  5  parts  in  100 
of  the  mineral  analyzed.  Therefore,  since  it  seemed  probable  to  me  that  the 
different  substances  might  not  have  been  well  washed,  or  that  the  analysis  might 
not  have  been  made  with  sufficient  precision  in  other  respects,  I  repeated  it 
twice  more  with  all  the  care  possible,  but  always  with  results  very  httle  differ- 
ent. I  obtained.  Silica.  78  45,  79.85,  Alumina:  17  20,  17.30;  Sulfate:  19.50, 
17,75,  At  last,  having  studied  this  sulfate  more  closely,  I  soon  found  that  it 
contained  a  definite  fixed  alkali,  whose  nature  had  not  previously  been 
known  (21). 

Petalite  is  now  known  to  be  lithium  aluminum  silicate,  LiAl(Si2O6)o 
On  April  22,  1818,  Berzelius  wrote  to  his  London  friend  Dr.  Marcet 
that  Arfwedson  had  also  found  lithium  in  spodumene  and  lepidolite,  and 
that  the  former  contains  about  8  per  cent  of  this  metal,  whereas  the  latter 
contains  about  4  per  cent.  In  the  spring  of  the  memorable  year  (1824) 
that  Friednch  Wohler  spent  at  Stockholm,  he  accompanied  a  distinguished 
group  of  Swedish  chemists,  including  Berzelius,  Wilhelm  Hisinger,  Arf- 
wedson, and  C,  Retzius,  on  a  holiday  excursion  to  Uto  Island,  about  two 
miles  out  from  shore  in  the  Baltic  Sea.  The  island  interested  them 
greatly,  not  only  because  of  its  rich  iron  mines,  but  also  because  of  its 
rare  minerals,  including  petalite  and  spodumene,  in  which  Arfwedson 
had  found  the  new  alkali  metal  (9).  Lepidolite  is  also  found  on  this 

island  (12). 

Arfwedson  also  studied  the  most  important  lithium  salts,  and  his 
results  were  quickly  confirmed  by  Vauquelin  (13).  Lithium  differs  from 
potassium  in  that  it  does  not  give  a  precipitate  with  tartaric  acid>  and 
from  sodium  in  that  its  carbonate  is  only  sparingly  soluble.  The  beautiful 
red  color  which  lithium  salts  impart  to  a  flame  was  first  observed  in  1818 
by  C,  G.  Gmelin  (14,  25). 

Arfwedson  and  Gmelin  tried  in  vain  to  isolate  lithium  metal.  After 
failing  to  reduce  the  oxide  by  heating  it  with  iron  or  carbon,  they  tried 
to  electrolyze  its  salts,  but  their  voltaic  pile  was  not  sufficiently  powerful 
(14).  W.  T.  Brande  succeeded  in  decomposing  lithia  with  a  powerful 
battery  and  obtained  a  white,  combustible  metal,  and  Davy  also  obtained 
a  small  amount  of  lithium  in  the  same  manner  (14S 15,  31,  32,  S3). 


488  DISCOVERY  OF  THE  ELEMENTS 

Although  these  early  investigators  obtained  only  an  extremely  small 
quantity  of  the  metal,  R  Bunsen  and  A.  Matthiessen  succeeded  in  1855 
in  preparing  enough  of  it  for  a  thorough  study  of  its  properties  (16). 
They  accomplished  the  reduction  by  heating  pure  lithium  chloride  in  a 
small  thick-walled  porcelain  crucible  with  a  spirit  lamp  such  as  Berzelius 
used,  while  a  current  from  four  to  six  carbon-zinc  elements  ( Bunsen  cells ) 
was  passed  through  the  molten  mass.  After  a  few  seconds  they  saw  a 
fused,  silver-white  regulus  form  at  the  cathode  and  build  up  in  two  or 
three  minutes  to  the  size  of  a  pea.  They  carefully  removed  the  globule 
with  an  iron  spoon,  placed  it  under  petroleum,  and  repeated  the  opera- 
tion eveiy  three  minutes  until  they  had  reduced  an  ounce  of  lithium 
chloride  (16)  They  also  showed  that  lithium,  although  it  was  first  found 
in  the  mineral  kingdom,  is  widely  distributed  in  all  three  of  the  natural 
realms. 

That  the  famous  mineralogist,  the  Abb6  Hauy,  held  Arfwedson  in 
high  esteem  is  evident  from  his  letter  of  June  13,  1820,  in  which  he  said 
to  Berzelius,  "Be  so  kind,  Monsieur,  as  to  offer  to  M.  Arfvedson,  of  whom 
it  suffices  to  say  that  he  is  your  worthy  pupil,  the  assurance  of  the  pro- 
found esteem  and  distinguished  respect  which  I  bear  him"  (17). 

In  the  same  year  Arfwedson  bought  an  ironworks  (forge  de  feu) 
and  a  large  estate  at  Hedenso  in  the  province  of  Sodermanland,  which 
caused  Berzelius  to  fear  lest  this  promising  young  chemist  might  abandon 
his  scientific  career  (17).  Perhaps  his  misgivings  were  well  founded, 
for  Thomas  Thomson,  after  mentioning  Aifwedson's  experiments  on  the 
oxides  of  uranium*  and  on  the  action  of  hydrogen  on  metallic  sulfates, 
said,  "He  has  likewise  analyzed  a  considerable  number  of  minerals  with 
great  care,  but  of  late  years  he  seems  to  have  lost  his  activity.  His 
analysis  of  chrysoberyl  does  not  possess  the  accuracy  of  the  rest;  by 
some  inadvertence,  he  has  taken  a  compound  of  glucina  and  alumina 
for  silica"  (18),  Arfwedson  died  at  his  Hedenso  estate  on  October  28, 
1841  (10). 

Gustaf  Flink  once  said  "Petalite  can  be  said  to  be  an  almost  ex- 
clusively Swedish  mineral,  for  in  foreign  localities,  Elba,  and  a  few  places 
in  North  America,  it  has  occurred  as  a  great  rarity.  In  the  Uto  mines, 
however,  it  occurs  in  well-nigh  inexhaustible  amounts"  (35),  The  first 
petalite  found  in  America  was  described  in  1824  by  Gerard  Troost,  a 
native  of  the  Netherlands,  who  studied  mineralogy  under  the  Abb6 
R.-J.  Hauy  and  later  became  a  naturalized  citizen  of  the  United  States, 
a  founder  of  the  Academy  of  Natural  Sciences  in  Philadelphia,  and  pro- 
fessor of  chemistry  at  the  Philadelphia  College  of  Pharmacy  (55).  When 
Dr.  Troost  analyzed  a  Canadian  mineral  presented  to  him  by  Dr.  Bigsby, 

*  See  Chapter  9,  p  267  and  Chapter  19,  pp.  500-01. 


THKEE  ALKALI  METALS  489 

he  found  that  an  alcoholic  solution  of  it  "burned  with  a  red  flame  of  a 
more  dense  colour  than  that  of  Strontian  .  .  .  Dr.  Bigsby  received  a  speci- 
men of  this  mineral  in  1820  from  Dr.  Lyons,  now  of  Montreal,  together 
with  other  rolled  rock  masses,  and  considered  it  a  Tremolite.  In  1823 
he  visited  the  locality  .  .  .  The  Petahte  occurs  on  the  north  shore  of  lake 
Ontario,  on  the  beach  in  front  of  York  [Toronto],  the  capital  of  Upper 
Canada,  a  few  yards  to  the  right  of  the  wharf  used  by  the  steamboat 
Frontinac  [sic]  ..."  (56). 

In  1823  Thomas  Nuttall  discovered  spodumene  at  Sterling,  Massa- 
chusetts. The  Journal  of  the  Philadelphia  Academy  of  Natural  Sciences 
for  1824  stated  that  "Mr,  Nuttall,  in  a  letter  to  Dr.  Hays,  dated  November 
22,  1823,  communicates  his  having  discovered,  whilst  on  a  mineralogical 
excursion  during  the  last  summer,  a  mineral  which  he  considers  to  be 
Spodumen  [sic].  As  this  mineral  had  never  been  previously  found  in 
the  United  States,  the  following  notice  will  probably  be  interesting.  The 
Spodumen  occurs  on  the  farm  of  Mr.  Putnam,  in  Sterling,  Massachusetts, 
where  it  is  found  abundantly  in  a  Granitic  rock,  composed  principally 
of  hyaline  Quartz  and  Mica,  the  Spodumen  supplying  the  place  usually 
occupied  by  Feldspar.  .  .  Mr.  George  Bo  wen,  who  examined  this 
mineral,  and  ascertained  that  it  contains  L'thia,  lately  discovered  the 
same  mineral  in  a  collection  of  specimens  from  the  vicinity  of  Deerfield, 
Massachusetts  .  .  ."  (57). 

Mr.  Bowen  fused  the  pulverized  mineral  with  caustic  potash,  dis- 
solved the  melt  in  hydrochloric  acid,  evaporated  the  solution  to  dryness, 
and  digested  the  residue  with  warm  alcohol  "That  it  was  reaUy  the 
muriate  of  lithia,"  said  Bowen,  "was  evident  from  its  tingeing  the  flame 
of  alcohol  of  a  deep  crimson  colour;  and  from  its  affording,  when  added 
to  a  concentrated  solution  of  carbonate  of  soda,  an  abundant  precipitate 
of  carbonate  of  lithia.  The  precise  locality  of  the  Spodumen  from  Deer- 
field,  I  am  not  able  to  point  out .  .  ."  (57). 

Lithium  in  Natural  Waters.  In  1825-26  Berzelius  determined  the 
lithium  content  of  several  mineral  waters  from  Bohemia  and  found  as 
much  as  a  centigram  of  lithium  carbonate  "in  every  bottle"  of  the  water 
from  the  Kreuzbrunn  Spring  at  Marienbad  (58,  59,  60).  One  of  the 
first  spectroscopic  analyses  ever  made  resulted  in  the  detection  of 
lithium  in  sea  water.  In  a  letter  to  Sir  Henry  Roscoe  written  on  Novem- 
ber 15,  1859,  Robert  Bunsen  mentioned  that  the  spectroscope  could  be 
used  to  determine  the  chemical  composition  of  the  sun  and  fixed  stars. 
"Substances  on  the  earth,"  he  added,  "can  be  determined  by  this  method 
just  as  easily  as  on  the  sun,  so  that,  for  example,  I  have  been  able  to 
detect  lithium  in  twenty  grams  of  sea  water"  (61). 

Lithium  in  Plants  and  Animals.  Although  Berzelius  and  Arfwedson 
named  the  new  alkali  lithia  because  it  was  first  discovered  in  the  mineral 


490  DISCOVERY  OF  THE  ELEMENTS 

kingdom,  it  was  found  to  exist  in  all  three  of  the  natural  realms.  In  1860 
G.  R.  Kirchhoff  and  Robert  Bunsen  detected  it  in  the  ash  of  the  grape, 
in  farm  products  from  the  Palatinate,  and  in  kelp  from  the  Gulf  Stream 
and  the  coast  of  Scotland  (58,  62}.  They  stated  that  "all  the  ashes  we 
investigated  of  wood  grown  on  granitic  soil  in  the  Odenwald,  as  well 
as  Russian  and  other  commercial  potashes,  contain  lithium.  Even  in 
the  ashes  of  tobacco,  of  the  grape  leaf,  vine,  and  grapes,  as  well  as  in 
the  ash  of  farm  products  which  were  raised  on  non-granitic  soils  in  the 
Rhine  Valley  near  Waghausel,  Deidesheim,  and  Heidelberg  and  in  the 
milk  of  animals  nourished  on  these  products,  lithium  is  not  lacking" 
(62,  63).  In  the  following  year  they  demonstrated  its  presence  spectro- 
scopicaUy  in  the  ash  of  the  milk  and  blood  of  animals  which  had  been  fed 
plants  from  the  Palatinate  (58,  64). 

In  1867  H.  Ritthausen  discovered  lithium  in  the  marl  and  arable  soil 
at  Weitzdorf,  East  Prussia  (5S,  63,  65).  Other  investigators  afterward 
detected  it  in  many  other  soils,  and  in  1915  L.  A.  Steinkoenig  and  W.  O. 
Robinson  found  it  to  be  present  in  every  American  soil  which  they  ana- 
lyzed (58,  66,  65). 

In  1918  these  two  chemists  and  C.  F.  Miller  analyzed  about  fifty 
samples  of  legumes,  grasses  (including  grains),  vegetables,  trees,  and 
shrubs  grown  in  nine  different  soils  of  known  composition  or  from 
localities  where  certain  rare  elements  were  known  to  occur.  Lithium 
was  found  in  spectroscopic  traces  in  all  the  plants  they  examined  (67). 

In  1880  C.  SchiappareUi  and  G.  Peroni  showed  that  lithium  also 
occurs  in  normal  human  urine  ( 65 ) ,  Alexandra  Desgrez  ( 1863-1940 )  and 
J.  Meumer  showed  in  1927  that  human  bones  and  teeth  contain  lithium 
phosphate  (69,  70). 

LITERATURE  CITED 

(1)  DAVY,  DR.  JOHN,  "The  Collected  Works  of  SIT  Humphry  Davy,  Bart.,  Vol    1, 

Smith,  Elder  and  Co  ,  London,  1839,  p.  117,    Quotation  from  Sir  H.  D. 

(2)  PARIS,  J.  A.,  "Life  of  Sir  Humphry  Davy,  Bart ,"  Vol.  1,  Colbura  and  Bentley, 

London,  1831,  pp  33-4.    Ode  to  St.  Michael's  Mount  in  Cornwall 

(3)  DAVY,  J.,  "The  Collected  works  of  Sir  Humphry  Davy,  Bart,"  ref.  (I ),  Vol.  1, 

pp,  10-1. 

(4)  Ifcid.,p.51. 

(5)  Ibid,  p.  88 

(6)  JAGNAUX,  R,,  "Histoire  de  la  Ctomie/'  Vol  2,  Baudry  et  Cie.,  Paris,  1891,  pp 

68-73. 

(7)  DAVY,  J.,  "The  Collected  Works  of  Sir  Humphry  Davy,  Bart.,"  ref.  ( 1 ),  Vol.  1, 

p.  109 

(8)  FARBER,  E,,  "Geschichtliche  Entwicklung  der  Chemie,"  Springer,  Berlin,  1921, 

pp    116-9 

(9)  WOHLER,  F,  "Early  recollections  of  a  chemist,"  Am    Chemist,  6,  131  (Oct., 

1875), 


THREE  ALKALI  METALS  491 

(10)  POGGENDORFF,   J.    C,    "Biographisch-Literarisches    Handworterbuch    ziir    Ge- 

schichte  der  exakten  Wissenschaften,"  6  vols.a  Verlag  Chemie,  Leipzig  and 
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(11)  SODERBAUM,  H.  G,,  "Jac.  Berzehus  Bref,"  Vol.  1,  part  1,  Almqvist  and  Wiksells, 

Upsala,  1912-1914,  pp,  63^t,  "Lettre  de  M.  Berzelius  a  M,  Berthollet  sur 
deux  Metaux  nouveaux,"  Ann.  chim.  phys.,  (2),  7,  199-201  (1818) 

(12)  SODERBAUM,  H   G,,  "Jac  Berzelius  Bref,"  ref.  (11),  Vol   1,  part  3,  pp   171-2 

(13)  VAUQUELIN,  NICOLAS-LOUIS,  "Note  sur  une  nouvelle  espece  d'Alcah  mineral," 

Ann  chim.  phys.,  (2),  7,  284-8  (1818). 

(14)  JAGNAUX,  R.,  "Histoire  de  la  Ghimie,"  ref.  (6),  Vol  2,  pp.  124-9. 

(15)  GMELIN,  L«,  "Handbuch  der  theoretischen  Chemie/*  ersten  Bandes  zweite  Ab- 

theilung,  dntte  Auflage,  F.  Varrentrapp,  Frankfurt  am  Main,  1826,  pp. 
597-8,  W.  T.  BRANDE,  "Manual  of  Chemistry,"  Vol.  2,  John  Murray,  London, 

1821,  p  57,  Scherer's  Allgem.  Nordische  Ann.  der  Chemie,  8,  120  ( 1822). 

(16)  BUNSEN,  R  ,  "Darstellung  des  Lithiums,"  Ann  ,  94,  107-10  (1855). 

(17)  SODERBAUM,  H.  G.,  "Jac.  Berzehus  Bref,"  ref.  (11),  Vol.  3,  part  2,  p.  165. 

(18)  THOMSON,  THOMAS,  "History  of  Chemistry,"  Vol.  2,   Colburn  and  Bendey 

London,  1831,  p.  229. 

(19)  GREGORY,  J.  C.,  "The  Scientific  Achievements  of  Sir  Humphry  Davy/*  Oxford 

University  Press,  London,  1930,  pp.  37-57. 

(20)  Ibid,  pp,  ui-vii  and  1-9. 

( 21 )  ARFWEDSON,  J.  A.,  "Analyses  de  quelques  mmeraux  de  la  mine  d'Uto  en  Suede, 

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82-107  (1819),  Afhandlingar  i  Kemi,  Fysik  och  Mmeralogie,  6,  (1818), 
Sci  News  Letter,  18,  No.  493,  186  (Sept  20,  1930). 

(22)  DAVY,  H.,  "The  decomposition  of  the  fixed  alkalies  and  alkaline  earths,"  Set, 

News  Letter,  14,  No.  390,  201-2  (Sept.  29,  1928) 

(23)  DAVY,  H,  "The  Decomposition  of  the  Fixed  Alkalies  and  Alkaline  Earths," 

Alembic  Club  Reprint  No.  6,  Univ.  of  Chicago  Press,  Chicago,  1902,  51  pp 

( 24 )  DAVY,  H.,  "The  Bakerian  lecture,  on  some  new  phenomena  of  chemical  changes 

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(25)  KOPP,  H.,  "Geschichte  der  Chemie,"  Vol.  4,   F.  Vieweg  und  Sohn,  Braun- 

schweig, 1847,  p  41. 

(26)  BROCKMAN,  C.  J.,  "Fused  electrolytes— an  historical  sketch,"  J.  Chem  Educ  ,  4, 

512-23  (April,  1927). 

(27)  COMBES,  A.,  "Second  letter  on  the  subject  of  the  new  metals,"  Nicholsons  ]., 

21,365  (SuppL,  1808). 

(28)  DAVY,  H.,  "Electro-chemical  researches,  on  the  decomposition  of  the  earths, 

with  observations  on  the  metals  obtained  from  the  alkaline  earths,  and  on  the 
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(29)  "Oeuvres  de  Lavoisier,"  Vol,  1,  Imprimerie  Imperiale,  Paris,  1864,  pp   119-20. 
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(31)  THOMSON,  T.,  "History  of  Chemistry,"  ref    (18),  Vol  2,  pp.  264-5;  Annafc?  of 

PMos,  (1),  12,  16  (July,  1818). 

(32)  WEEKS,  M  E.  and  M.  E.  LARSON,  "J.  A.  Arfwedson  and  his  services  to  chem- 

istry," J.  Chem.  Educ,  14,  403-7  (Sept,  1937). 
(S3)     ARFWEDSON,  J.  A.,  "Undersdkning  af  n&gre  mineralier,"  K  Vet.  Acad.  Handl , 

1822,  pp.  87-94,  Annals  of  PMos ,  23,  343-8  (May,  1824). 

(34)  DE  ANDRADA,  J  B.,  "Kurze  Angabe  der  Eigenschaften  und  Kennzeichen  einiger 

neuen  Fossilien  aus  Schweden  und  Norwegen,  nebst  einigen  chemischen 
Bemerkungen  uber  dieselben,"  Scherers  Allg.  J  der  Chemie,  4,  28-39 
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(35)  FLINK,  G,  "Bidrag  till  Sveriges  mineralogi,"  Arkiv  for  Kemi,  Mineralogi  och 

Geologi,  5,  21,  221-2  (1914). 


492  DISCOVERY  OF  THE  ELEMENTS 

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Sci.,  (2),  23,  99  (1857). 

(37)  VAUQT^LIN,  NICOLAS-LOUIS,  Schw.  /.,  21,  397-401  (1817) 

(38 )  SODERBAUM,  H  G.,  ref.  (11),  Vol,  8,  pp  50-1.    Letter  of  Berzelius  to  Hisinger, 

Jan   12,  1818. 

(39)  GMELIN,  C.  G,  "Analysis  of  petalite  and  examination  of  the  chemical  prop- 

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Sweden/7  Annals  of  Phiios.,   11,  196-8    (March,    1818);   Ibid.,   11,   365-6 
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(41)  NEIVA,  VENANGIO  DE  FIGUEIREDO,  "Rezumo  Biografio  de  Joze  Bonifacio  de 

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(42)  KQPP,  H  ,  ref.  (25),  Vol.  4,  pp.  3-41 

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Latin  of  Sir  Torbern  Bergman,"  Vol    1,  J.  Murray,  Balfour,  Gordon,  and 
Dickson,  London,  1784,  p.  21,  ibid ,  VoL  2,  footnote  to  p  438. 

(44)  BOHNIUS,  D.  JOH.,  "Dissertationes  Chymico-Physicae,"  Thomas  Fntsch,  Leip- 

zig, 1696,  pp  381-2. 

(45)  BOERHAAVE,  H.,  "Siemens  de  Chymie/'  Vol.  1,  Chardon,  fils,  Pans,  1754,  pp 

188,  197. 

(46)  DU  HAMEL  DU  MONCEAU,  H.-L.,  "Ueber  die  Basis  des  Seesalzes/'  CrelTs  Neues 

chem  Archiv.,  4,  166-70  (1785),  Hist,  de  I'acad.  roy.  des  sciences  (Paris), 
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(47)  "Recueil  des  memoires  de  chymie  .  .  .  dans  les  actes  de  Tacad,  des  sci.  de 

Stokolm  (sic)    .    .    ./'  Vol.  2,  pp.  515-7,  G.  BRANDT,  "Observations  et  ex- 
pe"nences  stir  les  differences  qui  se  trouve  entre  la  soude  et  la  potasse,"  Mem 
de  I'acad.  roy  de  Suede,  Vol.  8  ( 1746 ) . 

(48)  MARGGRAF,  A.  S.7  "Chymische  Schriften,"  revised  ed.,  Vol.  1,  Arnold  Wever, 

Berlin,  1768,  pp  134-78 

(49)  Obituary  of  Edward  Daniel  Clarke,  Annual  Register,  1822,  pp   274-6 

(50)  BROWNE,  C    A.,  "Historical  notes  upon  the  domestic  potash  industry  in  early 

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(51)  FLETCHER,  J.  C.  and  D.  P,  KIDDER,  "Brazil  and  the  Brazilians  .    .    ,/'  Little, 

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(53)  "Grande  enciclope'dia  portuguesa  e  brasilerra,"  Vol.  2,  Editorial  Enciclopedia, 

Ltd.,  Lisbon  and  Rio  de  Janeiro,  not  dated,  pp   525-6 

(54)  "Nouvelle  biographie  gen£rale,"  Vol.  2,  Firrmn  Didot  Freres,  Paris,    1855, 

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(57)  "Notices  of  American  spodumene,"  ibid.,  3,  (2),  284-6  ( 1824). 

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Annals  of  Philos.f  new  series,  11,  69,  145-6  (Jan.,  Feb.,  1826). 

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July  5,  1825. 

( 61 )  OSTWALD,  WILHELM,  "Manner  der  Wissenschaft.    R.  W.  Bunsen,"  Verlag  von 

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THREE  ALKALI  METALS  493 

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( 71 )  REILLY,  DESMOND,  "An  Irish- American  chemist,  William  James   MacNeven, 

1763-1841,"  C/ij/mfa,  2,  17-26  (1949) 

(72)  ANON  ,  "Life  of  William  Allen,  with  selections  from  his  correspondence,"  Vol. 

1,  Henry  Longstreth,  Philadelphia,  1847,  p.  66. 


Courtesy  Mr.   Carl  Bjdrkbom,   Royal  Library,   Stockholm 

Johan  August  Arfwedson>  1792-1841.  This  lithograph  by 
Fehr  and  Miiller  o£  Stockholm  was  labeled  by  Berzelius 
"Reskamraten  Arfvedson"  (traveling  companion  Arfvedson). 
Berzelius  placed  it  in.  the  manuscript  o£  his  travel  diary 

"Reseanteckningar . " 


19 

J.  A.  Arfwedson  and  his  service  to  chemistry 

Although  the  histories  of  chemistry  devote  but  little  space  to  the 
work  of  J.  A.  Arfwedson,  the  discoverer  of  lithium,  Berzelius' 
correspondence,  travel-diary,  and  autobiography  contain  much 
interesting  information  about  him.  The  superb  biography  of 
Berzelius  which  H.  G.  Soderbaum  completed  near  the  close  of 
his  life  also  throws  much  light  on  Arfwedsons  chemical  activity. 

J  ohan  August  Arfwedson  was  born  in  January,  1792,*  (I,  2), 
on  the  family  estate  at  Skagerholms-Bruk  in  Skaraborg  County.,  Sweden. 
Until  the  age  of  fourteen  he  was  educated  at  home,  and  in  1806  he 
entered  the  college  (hogskolan)  at  Upsala.  After  completing  the  mining 
course  at  Upsala  and  the  mining  examination,  he  entered  the  Royal 
Bureau  of  Mines  at  Stockholm,  where  he  served  as  secretary  at  the 
Bureau,  and  still  found  time  to  carry  on  research  in  chemical  analysis 
in  Berzelius'  famous  laboratory.  When  the  twenty-five-year-old  Arfwed- 
son entered  this  laboratory  early  in  1817,  he  had  among  his  classmates 
Count  H.  G.  Trolle-Wachtmeister,  ten  years  his  senior,  and  Lieutenant 
C.  A.  Arrhenius,  the  discoverer  of  gadolinite,  who  was  then  sixty  years 
of  age. 

Arfwedson  immediately  set  to  work  analyzing  meionite  and  leucite 
(3,  4,  5).  He  observed  that  although  the  leucite  was  very  infusible, 
the  meionite  melted  readily  before  the  blowpipe,  swelled,  and  formed 
an  enamel.  Since  his  analysis  of  meionite  agreed  closely  with  Klaproth's 
analysis  of  leucite,  Arfwedson  analyzed  a  specimen  of  leucite  and 
found  these  two  minerals  to  be  very  similar  in  composition,  except  that 
the  leucite  contained  no  lime.  Suspecting,  therefore,  that  the  lime  must 
be  the  cause  of  the  meionite's  fusibility,  he  mixed  a  little  lime  with  the 
leucite,  after  which  it,  too,  could  be  easily  melted. 

In  the  autumn  of  the  same  year,  Arfwedson  completed  a  beautiful 
research  on  the  oxides  of  manganese.  He  determined  the  per  cent  of 

This  chapter  was  originally  presented  by  Mary  E.  Larson  and  the  author  before  the 
Divisions  of  History  of  Chemistry  and  Chemical  Education  at  the  Midwest  Regional 
Meeting  of  the  A.  C.  S.,  Omaha,  Nebraska,  April  30,  1937. 

*  Soderbaum  (1)  and  Leijonhufvud  (2)  give  the  date  of  Arfwedson's  birth  as  January 
4th;  the  unsigned  obituary  (4)  in  the  Kongl  Vet.  Acad.  Handl.  gives  it  as  January  12th 

495 


496  DISCOVERY  OF  THE  ELEMENTS 

manganese  in  the  brown  powder  obtained  by  igniting  manganous  oxide 
and  in  the  black  powder,  manganic  oxide,  obtained  by  evaporating  this 
brown  manganosic  oxide  with  nitric  acid  and  gently  igniting  the  residue. 
Since  he  found  it  difficult  to  get  the  black  powder  of  constant  composition, 
he  recommended  that  in  analytical  work  the  oxide  should  always  be 
strongly  ignited  and  weighed  as  manganosic  (mangano-manganic) 
oxide,  Mn3O4. 

Arfwedson  also  observed  that  the  ratio  of  the  oxygen  in  manganous 
oxide  to  the  oxygen  in  manganic  oxide  is  as  1  to  I1/*  a  relation  which 
the  modern  chemist  expresses  in  the  formulas  MnO  and  Mn2O3.  He 
realized  that  manganosic  oxide  must  be  a  compound  of  these  two  oxides, 
and  reasoned  that  "if  this  compound,  like  ferrous-ferric  oxide,  may  be 
supposed  to  be  of  such  composition  that  the  oxide  contains  twice  as  much 
metal  and  three  times  as  much  oxygen  as  the  protoxide,  this  compound 
consists  of  72.82  per  cent  metal  and  27.18  per  cent  oxygen.  ...  I  have 
called  this  oxide  oxidum  manganoso-manganicum  because  of  its  resem- 
blance to  ferroso-ferric  oxide,  the  composition  of  which  Herr  Professor 
Berzelius  described  in  his  'Attempt  to  lay  the  foundations  of  a  purely 
scientific  system  for  Mineralogy/  page  92," 

Manganosic  oxide  is  now  known  to  contain  only  72.03  per  cent  of 
manganese.  Since  Arfwedson  obtained  1.0735  grams  of  manganosic 
oxide  to  the  oxygen  in  manganic  oxide  is  as  1  to  l1/^  a  relation  which 
ment  with  the  value  now  accepted  (1.0752  grams),  his  experimental 
work  must  have  been  excellent.  In  computing  the  per  cent  of  manganese 
in  manganosic  oxide,  however,  he  made  the  mistake  of  accepting  21.88 
per  cent  as  the  oxygen  content  of  manganous  oxide,  a  value  which  Pro- 
fessor Johann  Friedrich  John  of  Berlin  had  obtained  by  the  analysis  of 
manganous  sulfate.  Arfwedson  determined  the  composition  of  manga- 
nous oxide  by  passing  hydrogen  chloride  over  a  weighed  portion  of 
manganous  carbonate,  treating  the  resulting  manganous  chloride  with 
an  excess  of  silver  nitrate,  and  weighing  the  silver  chloride.  Although 
his  value  of  22.14  per  cent  oxygen  in  manganous  oxide  was  somewhat 
better  than  that  of  John  (the  value  now  accepted  is  22.56  per  cent), 
Arfwedson  lacked  confidence  in  it  and  stated,  "I  have  reason  to  suspect 
a  slight  admixture  of  oxide  in  the  muriate  I  investigated,  and  therefore 
the  result  of  my  analysis  is  probably  less  reliable."  In  September,  1817, 
Berzelius  reported  Arfwedson's  research  in  letters  to  Dr.  Marcet  and  Gay- 
Lussac  (6),  and  in  the  following  year  Arfwedson  published  it  in  the 
Afhandlingar  i  Fysik,  Kemi  och  Mineralogi  (7),  the  editorial  staff  of 
which  he  had  recently  joined. 

When  he  had  completed  the  manganese  research,  Berzelius  set  him 
to  work  at  analyzing  a  new  mineral,  petalite,  from  the  iron  mine  on 
Uto,  one  of  the  many  rocky  islands  or  skerries  which  comprise  Stock- 


J.  A.  ARFWEDSON  AND  HIS  SERVICE  TO  CHEMISTRY  497 

holm's  superb  archipelago.  Arfwedson  fused  the  petalite  with  potassium 
carbonate,  determined  the  silica  in  the  usual  manner,  and  precipitated 
the  alumina  with  ammonium  carbonate.  His  analysis  totaled  only  96 
per  cent.  Surprised  to  find  such  a  large  loss  in  such  a  simple  analysis,  he 
decomposed  the  petalite  with  barium  carbonate.  After  removing  the 
silica  and  alumina  and  the  barium  sulfate  obtained  by  adding  excess 
sulf'uric  acid,  he  evaporated  the  washings,  volatilized  the  ammonium 
salts,  and  found  a  fused  residue  of  a  soluble,  non-volatile  sulfate.  Since 
an  aqueous  solution  of  this  salt  gave  no  precipitate  with  tartaric  acid, 
"platina  solution,"  or  caustic  potash,  the  base  could  be  neither  potash  nor 
magnesia.  Arfwedson  therefore  assumed  that  the  salt  must  be  sodium 
sulfate,  but  when  he  calculated  his  results  on  that  assumption,  his  analysis 
totaled  about  105  per  cent.  Thinking  that  this  excess  weight  must  be  due 
to  improper  washing  of  his  precipitates,  he  repeated  the  analysis  twice 
and  obtained  in  duplicate  determinations  19.500  and  17.75  per  cent  of 
the  unknown  sulfate. 

In  a  letter  to  Wilhelm  Hisinger,  who  was  then  analyzing  the  same 
mineral,  Berzelius  wrote  on  January  12,  1818,  "...  All  these  facts  have 
led  us  to  believe  that  petalite  perhaps  contains  a  new  alkali  ...  of  such 
great  saturating  capacity  that,  when  the  salt  is  computed  as  a  sodium 
salt,  the  excess  in  weight  arises  through  the  fact  that  the  salt  contains 
much  less  base  than  a  sodium  salt.  If  this  be  true,  Arfwedson  has  had  the 
good  fortune  to  make  in  his  second  mineralogical  analysis  one  of  the  most 
remarkable  discoveries  which  can  be  made  in  this  manner  .  .  /'  (3). 
Berzelius  also  announced  Arfwedson's  discovery  of  lithium  to  Dr.  Marcet 
and  Count  Berthollet  in  the  same  letters  in  which  he  mentioned  his  own 
discovery  of  selenium  (8).  Arfwedson's  announcement  of  the  discovery 
was  published  in  the  Afhandlingar  in  the  same  year  (9).  According 
to  Dr.  Soderbaum  (3),  Berzelius  himself  deserves  a  great  deal  of  credit 
for  discovery  of  lithium  as  well  as  selenium,  but  was  generous  enough  to 
let  the  lithium  research  be  published  under  Arfwedson's  name  alone. 

Arfwedson  prepared  lithium  acetate,  ignited  it,  and  noted  the  in- 
solubility of  the  resulting  lithium  carbonate  in  water  and  its  action  on 
platinum.  He  also  prepared  and  studied  the  bicarbonate,  sulfate,  nitrate, 
chloride,  tartrate,  borate,  hydroxide,  and  a  double  sulfate  which  he  re- 
ported as  lithium  alum.  He  mentioned  that  lithium  hydroxide  is  much 
less  soluble  than  the  other  caustic  alkalies  and  that  it  has  a  greater 
"saturation  capacity'*  [lower  equivalent  weight]  than  they.  Because  of 
its  ability  to  form  deliquescent  salts  with  nitric  and  hydrochloric  acids, 
Arfwedson  recognized  the  close  relation  between  the  new  alkali  and  the 
alkaline  earths,  especially  magnesia. 

His   attempt  to  decompose  the  new  base  with  Berzelius'   galvanic 
battery  of  fifty  pairs  of  plates  in  an  electrolyte  of  sodium  chloride  was 


498  DISCOVERY  OF  THE  ELEMENTS 

unsuccessful.  As  early  as  1818,  however,  Sir  Humphry  Davy  obtained 
a  minute  amount  of  lithium  metal  (10).  When  he  passed  a  current 
through  fused  lithium  carbonate  in  a  platinum  capsule,  "the  alkali  de- 
composed with  bright  scintillations,  and  the  reduced  metal  being  sepa- 
rated, afterward  burnt.  The  small  particles  which  remained  a  few 
moments  before  they  were  reconverted  into  alkali  .  .  .  were  .  .  .  very 
similar  to  sodium.  A  globule  of  quicksilver,  made  negative  and  brought 
into  contact  with  alkaline  salt,  soon  became  an  amalgam  of  lithium,  and 
had  gained  the  power  of  acting  on  water.  .  .  /' 

Most  standard  works  of  reference  also  contain  incomplete  statements  that 
lithium  was  isolated  by  Brande  (or  Brandes)  and  refer  to  Setter,,  8,  120  or 
Schweigger's  J.,  8,  120.  The  correct  reference  is  Scherer's  Allgemeine 
Nordische  Annalen  der  Chem.,  8,  120  (1822),  which  merely  states  that  W. 
T.  Brande  used  a  voltaic  pile  to  prepare  lithium  as  a  shining,  white,  combust- 
ible metal  and  refers  to  the  second  London  edition  of  his  "Manual  of  Chem- 
istry/' Volume  2,  page  57.  This  edition  was  published  by  John  Murray  in 
1821.  Branded  complete  statement  therein  is  as  follows:  "When  lithia  is  sub- 
mitted to  the  action  of  the  Voltaic  pile,  it  is  decomposed  with  the  same  phe- 
nomena as  potassa  and  soda;  a  brilliant  white  and  highly  combustible  metallic 
substance  is  separated,  which  may  be  called  lithium,  the  term  lithia  being  ap- 
plied to  its  oxide.  The  properties  of  this  metal  have  not  hitherto  been  investi- 
gated, in  consequence  of  the  difficulty  of  procuring  any  quantity  of  its  oxide."* 

In  1821  Arfwedson  published  a  supplementary  note  to  his  lithium 
research  (11),  in  which  he  stated  that  the  salt  which  he  had  previously 
reported  as  lithium  acid  sulfate  must  be  the  normal  sulfate  and  that  the 
double  sulfate  he  had  at  first  taken  for  lithium  alum  was  really  potassium 
alum  resulting  from  a  trace  of  potassium  in  his  alumina. 

In  the  summer  of  1818  Arfwedson  went  to  England,  taking  with  him 
specimens  of  Berzelius'  new  element  selenium  to  present  to  Dr.  Marcet, 
Sir  Humphry  Davy,  and  Dr.  W.  H.  Wollaston  as  gifts  from  the  discoverer. 
Berzelius  met  him  there  later  and  accompanied  him  on  visits  to  Dr. 
Wollaston,  William  Prout,  Sir  Joseph  Banks,  F.  C.  Accum,  William  Allen, 
and  the  geologist  John  Farey,  Senior.  In  company  with  Berzelius  he 
studied  at  first  hand  the  soda  water,  gas,  and  brewing  industries  of 
England.  In  October  of  the  same  year  the  aged  Abbe  R.-J.  Haiiy  of 
Paris  entertained  Berzelius  and  Arfwedson  and  gave  them  some  inspiring 
lessons  on  mineralogy  (12). 

In  June,  1819,  Berzelius,  Arfwedson,  Alexandra  and  Adolphe  Bron- 
gniart,  and  several  other  scientists  made  a  geological  tour  of  the  Fontaine- 
bleau  Forest  and  the  country  surrounding  Clermont  Part  of  the  journey 
was  made  in  a  crowded  diligence  in  which  "Arfwedson's  slender  form 
became  still  more  compressed."  At  the  inn  in  Clermont,  Arfwedson, 
*  This  may  serve  as  a  correction  to  "The  Discovery  of  the  Elements,"  3rd  ed.a  p.  125, 


J.  A.  ARFWEDSON  AND  HIS  SERVICE  TO  CHEMISTRY  499 


Berzelius'  Blowpipe  Lamp 


From  Berzelius*  "Lehrbuch  der  Chemie" 

N.  V.  Almroth,  and  Berzelius  finally  relinquished  one  of  their  two  wax 
candles  to  the  insistent  maid  servant,  who  needed  it  for  another  guest,  and 
continued  their  studies  by  the  light  of  Berzelius'  famous  blowpipe  lamp. 

The  Mont-Dore  region  could  be  explored  only  on  horseback.  "I 
cannot  mention/'  said  Berzelius,  "  all  the  troubles  I  had  (I)  in  getting 
my  left  foot  up  into  its  stirrup  and  (2)  in  throwing  the  right  one  so 
high  up  into  the  air  that  it  arrived  right  over  the  little  portmanteau 
which  was  tied  back  of  the  saddle.  .  .  .  However,  after  several  attempts, 
and  after  Almroth  and  Arfwedson  had  laughed  to  their  hearts'  content 
at  my  awkwardness,  I  finally  succeeded." 

On  their  journey  to  le  Puy,  their  fellow  passengers  were  good 
natured,  inquisitive  peasants  who  thought  the  Swedish  language  was 
a  kind  of  French  patois.  "Arfwedson,"  said  Berzelius,  "was,  in  their 
opinion,  a  prince,  for  he  was  wearing  in  the  cabriolet  the  same  suit  he 
wore  on  the  streets  of  Paris,  whereas  Almroth  and  I  had  adapted  ourselves 
more  to  the  dirty,  careless  traveling  costume  of  the  French." 

In  Lyons,  Arfwedson  and  Berzelius  observed  the  manufacture  of 
silk  and  velvet  in  the  homes  of  the  workers.  In  Geneva  they  visited  Dr. 
and  Mrs.  Alexandre  Marcet  While  they  were  in  Zurich,  Professor  M.  A. 
Pictet  of  Geneva  announced  to  them  that  they  had  both  been  elected  to 
honorary  membership  in  the  Helvetian  Scientific  Society. 

To  simplify  their  journey  across  Prussia  and  homeward  through 
Sweden,  Arfwedson  bought  a  fine  carriage  in  Dresden.  Berzelius  and  he 
visited  the  porcelain  works  at  Berlin,  where  Berzelius  bought  several 
porcelain  stopcocks  and  was  delighted  to  find  them  completely  airtight. 


500  DISCOVERY  OF  THE  ELEMENTS 

After  their  return  to  Stockholm  in  the  winter  of  1819,  Arfwedson  set 
up  his  own  laboratory  and  equipped  it  with  apparatus  he  had  bought 
during  his  travels.  In  the  following  year  he  purchased  a  handsome  estate 
at  Hedenso  (Heden's  Island),  where  he  equipped  another  chemical 
laboratory.  However,  since  he  owned  the  Nashulta  Works  and  mill  in 
Sodermanland  near  Hedenso  and  shares  in  the  Gravendal  Works  in 
Kopparberg  and  industrial  plants  at  Skagerholm  and  Brunnsberg,  his 
executive  duties  left  him  little  time  for  research. 

On  April  18,  1821,  he  was  elected  to  membership  in  the  Swedish 
Academy  of  Sciences.  In  the  same  year  he  published  some  analyses  of 
cyanite  from  St.  Gotthard  and  Roras  and  nepheline  and  sodalite  from 
Vesuvius  (13).  In  1822  he  published  analyses  of  cinnamon  stone, 
chrysoberyl,  and  boracite  (14).  He  found  the  cinnamon  stone  which 
Berzelius  had  brought  back  from  Vermland  to  be  a  calcium  aluminum 
iron  silicate  and  regarded  it  as  a  true  garnet  like  the  one  from  Ceylon 
which  Klaproth  had  analyzed. 

Arfwedson's  analysis  of  Brazilian  chrysoberyl  was  severely  criticized 
by  Thomas  Thomson,  who  said  that  "by  some  inadvertence,  he  has  taken 
a  compound  of  glucina  and  alumina  for  silica"  (15).  Glucina,  or  beryllia, 
had  been  discovered  by  N.-L.  Vauquelin  24  years  before  (16). 

Arfwedson  fused  the  chrysoberyl  three  times  with  caustic  potash 
in  a  silver  crucible.  Since  a  portion  of  the  melt  corresponding  to  about 
18  per  cent  of  the  mineral  failed  to  dissolve  in  hydrochloric  acid,  he 
reported  this  residue  as  silica.  It  is  now  known  that  beryllium  hydroxide, 
when  freshly  precipitated,  dissolves  readily  in  hydrochloric  acid,  but 
becomes  after  a  time  almost  completely  insoluble  in  it  (17).  Therefore, 
it  is  probable  that  Arfwedson's  "silica"  was  really  the  beryllium  hydroxide. 
He  then  precipitated  the  alumina  by  adding  ammonium  hydroxide  to 
the  acid  filtrate.  To  satisfy  himself  of  the  purity  of  his  alumina,  he 
saturated  the  alkaline  solution  with  hydrochloric  acid  until  the  precipitate 
dissolved,  and  added  a  large  excess  of  ammonium  carbonate.  "Had  any 
glucina  [beryllia]  or  yttria  existed  in  the  matter,"  said  Arfwedson,  "it 
would  have  been  dissolved  by  this  excess  of  carbonate  of  ammonia,  and 
would  have  fallen  when  the  filtered  liquid  was  boiled  till  the  excess  of 
ammonia  was  driven  off;  but  the  liquid  stood  this  test  without  any 
precipitate  appearing."  Arfwedson  was  evidently  unable  to  detect 
beryllia  here  because  he  had  already  filtered  it  off  and  reported  it  as 
silica.  When  American  chemist  Henry  Seybert  analyzed  the  same  mineral 
in  1824  he  found  it  to  contain  15  to  16  per  cent  of  beryllia  (22). 

In  1822  Arfwedson  published  his  paper  on  uranium  (18).  More 
than  thirty  years  before,  M.  H.  Klaproth  had  heated  a  paste  made  with 
uranic  oxide  and  linseed  oil,  and  obtained  a  brown  powder  with  a 
metallic  luster,  which  he  regarded  as  metallic  uranium.  Although  others 


J.  A.  ARFWEDSON  AND  HIS  SERVICE  TO  CHEMISTRY 


501 


had  used  carbon  crucibles  in  their  attempts  to  reduce  uranium  oxide  to 
the  metal,  Arfwedson  used  hydrogen.  He  placed  a  weighed  portion 
of  ignited  "uranous  oxide"  [uranosic,  or  uranous-uranic  oxide]  in  a 
bulb  blown  out  at  the  center  of  a  piece  of  barometer  tubing,  drove  off  the 
moisture,  and  passed  dry  hydrogen  over  it.  As  soon  as  the  air  had  been 
removed,  he  heated  the  bulb  with  an  Argand  spirit  lamp.  A  vigorous 
reaction  took  place,  and  in  a  few  minutes  the  green  "uranous  oxide" 
had  been  changed  to  "a  powder  of  a  liver-brown  color,"  which  Arfwedson 
believed  to  be  uranium  metal. 

He  also  prepared  the  "potash  muriate  of  uranium"  [potassium  uranyl 
chloride,  K2(UO2)Cl4],  and  attempted  to  analyze  it  by  reduction  with 
hydrogen  just  as  Berzelius  had  analyzed  potassium  chloroplatinate  (19). 
As  Arfwedson  passed  hydrogen  over  the  strongly  heated  salt,  it  continued 
to  lose  hydrochloric  acid  for  more  than  two  hours.  After  cooling  the 
apparatus,  he  washed  out  the  potassium  chloride  and  the  undecomposed 
salt  and  obtained  a  dark,  crystalline  powder  with  a  metallic  luster. 
When  this  was  heated,  it  became  converted  into  green  "uranous^  oxide^ 
[uranosic  oxide].  During  this  change,  100  parts  of  the  so-called  "metal" 
[uranous  oxide]  gained  3.7  parts  of  oxygen.  This  was  evidently  the 
reaction:  3UO2  +  O2  —  U3O8,  in  which  100  parts  of  uranous  oxide 
actually  gain  3.95  parts  of  oxygen;  100  parts  of  true  uranium  metal  would 
have  gained  17.9  parts  of  oxygen.  Arfwedson,  however,  did  not  believe 
that  his  powder  could  be  an  oxide,  for,  according  to  Sir  Humphry  Davy's 
new  theory  regarding  the  composition  of  muriatic  [hydrochloric]  acid,  the 
double  chloride  of  uranium  and  potassium  contained  no  oxygen. 

Although  Arfwedson,  Klaproth,  Berzelius,  and  many  other  eminent 
chemists  long  regarded  this  crystalline  powder  as  the  metal,  E.  M.  Peligot 
in  1841  obtained  the  true  metal.  When  he  heated  uranous  oxide  with 
carbon  in  a  current  of  chlorine,  he  obtained  carbon  monoxide,  carbon 
dioxide,  and  a  green  crystalline  compound  which  is  now  known  to  be 
uranous  chloride,  UC14.  Since  the  evolution  of  carbon  dioxide  and  carbon 
monoxide  showed  that  the  so-called  "uranium"  must  contain  oxygen, 
Peligot  heated  the  uranous  chloride  with  potassium  and  succeeded  for 
the  first  time  in  preparing  and  studying  true  metallic  uranium.  As  early 
as  1824,  however,  Friedrich  Stromeyer  had  doubted  that  Arfwedson's 
"uranium"  was  the  metal  (23}. 

When  Arfwedson  tried  to  analyze  lead  uranate  by  reducing  it  with 
hydrogen,  it  gained  weight  and  became  hot.  When  he  placed  the  reduced 
mass  on  paper,  he  was  astonished  to  see  it  burst  into  flame.  He  also  pre- 
pared other  pyrophoric  alloys  of  uranium  in  the  same  way.  "The  uranium 
alloys,"  said  he,  "absorb  oxygen  again  at  ordinary  temperatures,  become 
ignited,  and  thus  constitute  a  peculiar  kind  of  pyrophors  which  are  not 
inferior  in  flammability  to  those  already  known." 


502  DISCOVERY  OF  THE  ELEMENTS 

In  1822  Arfwedson  published  a  paper  on  the  decomposition  of 
sulfates  with  dry  hydrogen  (20).  In  the  following  year  the  British 
mineralogist  H.  J.  Brooke  (1771-1857)  described  a  new  mineral,  arfwed- 
sonite  (21).  "The  benefits  which  mineralogy  has  derived  from  the 
labours  of  Mr.  Arfwedson/'  said  he,  "have  induced  me  to  associate  his 
name  with  this  mineral,  which  is  from  Greenland,  and  is  black  and 
foliated,  and  has  been  hitherto  called  ferriferous  hornblende.  .  .  /' 

In  the  autumn  of  1824  Arfwedson  helped  Berzelius  and  Wilhelm 
Hisinger  arrange  the  mineral  collection  of  the  Academy  of  Sciences  ac- 
cording to  Berzelius*  chemical  system.  Two  years  later  Berzelius  visited 
Arfwedson  at  Hedenso.  "This,"  said  he,  "is  a  most  beautiful  place,  and 
Arfwedson  and  his  wife  have  improved  it  since  I  was  here  last  time. 
Inside  there  reigns  extreme  neatness  and  a  degree  of  luxury  which  could 
be  much  less  and  still  be  sufficient"  ( 3 ) .  *  Berzelius'  pleasure  was  marred, 
however,  by  an  attack  of  gout  which  did  not  yield  even  when  Arfwedson 
himself  applied  nine  leeches  to  the  affected  knee. 

Although  Arfwedson's  business  interests  more  and  more  distracted 
his  attention  from  chemical  research,  this  was  not  caused  by  the  love  of 
money.  When  one  of  his  uncles  bequeathed  him  the  magnificent  Forssby 
estate  with  its  precious  collection  of  oil  paintings,  Arfwedson  allowed  this 
inheritance  to  be  shared  according  to  law  with  the  other  heirs. 

In  the  last  year  of  his  life,  the  Swedish  Academy  of  Sciences  awarded 
him  its  large  gold  medal  (2)  in  honor  of  his  discovery  of  lithium.  He  died 
at  Hedenso  on  October  28,  1841,  and  was  survived  by  his  wife  and  three 
sons.  The  Vetenskapsacademiens  Handlingar  for  that  year  contained  the 
following  tribute  to  his  memory:  "His  love  of  order  gave  an  impress  of 
neatness  not  only  to  his  person  but  also  to  everything  about  him.  He  had 
a  pleasant  manner;  when  different  points  of  view  were  exchanged,  he  ex- 
pressed himself  with  a  deliberateness  which  was  not  compliance  and  with 
a  thoroughness  which  showed  deep  thought.  One  may  venture  to  say  that, 
because  he  was  obliged  to  devote  his  time  to  the  management  of  a  con- 
siderable fortune,  ...  the  science  to  which  he  devoted  himself  in  his 
youth  lost  much  (4)." 

In  conclusion  we  wish  to  thank  Mr.  Carl  Bjorkbom  of  the  Royal 
Library  at  Stockholm  and  Miss  Amy  Wastfelt  of  Upsala  for  their  kind  as- 
sistance. 

LITERATURE  CITED 

(1)  BOETHIUS,   B.,   "Svenskt  biografiskt  lexikon,"   A.   Bonnier,   Stockholm,   1918. 

Article  on  Arfwedson  by  H.  G.  Soderbaum. 

(2)  LEIJONHUFVUD,  K.  A.  K:SON,  "Ny  svensk  slaktbok,"  P.  A.  Norstedt  &  Soner, 

Stockholm,  1906,  pp.  94-5. 

(3)  SODERBAUM,  H.  G.,  "Berzelius  levnadsteckning,"  3  vok,  Almqvist  &  Wiksells 

Boktryckeri  A.-B.,  Upsala,  1929-31. 
*  Letter  of  Berzelius  to  Carl  Palmstedt,  July  26,  1826, 


J.  A.  ARFWEDSON  AND  HIS  SERVICE  TO  CHEMISTRY  503 

(4}  ANON.,  "Biografi  ofver  Johan  August  Arfvedson,  Brukspatron,"  Kongl  Vet. 
Acad.  Handl,  1841,  pp.  249-55.  o  .  „ 

(5)  ARFWEDSON,  J.  A.,  "Analys  af  meionit  dioctaedre  och  af  leucit  fran  Vesuvius, 

•  Afh.  i  Fysik,  Kemi  och  Minerdogi,  6,  255-62  (1818). 

(6)  SODERBAUM,  H.  G.,  "Jac.  Berzelius  Bref,"  Vol.  1,  part  3,  Almqvist  &  Wiksells, 

Upsala,  1912-1914,  pp.  158-9.  Letter  of  Berzelius  to  Marcet,  Sept.  23, 
1817;  Ann.  chim.  phys.,  (2),  6,  204-5  (1817).  Letter  of  Berzelius  to  Gay- 
Lussac,  Sept.  28,  1817. 

(7}  ARFWEDSON,  J.  A.,  "Undersoknfng  af  oxidum  manganoso-manganicum,  en 
hittills  okand  kemisk  forening  af  manganoxidul  och  oxid,"  Afh.  i  Fysik,  Kemi 
och  Min.,  6,  222-36  (1818);  Annals  of  Philos.,  23,  267-75  (Apr.,  1824). 

(8)  SODERBAUM,  H.  G.,  "Jac.  Berzelius  Bref,"  Vol.  1,  part  1,  Almqvist  &  Wiksells, 

Upsala,  1912-14,  pp.  6.3-4.  Letter  of  Berzelius  to  BerthoUet,  Feb.  9,  1818; 
ibid.,  Vol.  1,  part  3,  p.  160.  Letter  of  Berzelius  to  Dr.  Marcet,  Feb.  6,  1818. 

(9)  ARFWEDSON,  J.  A.,  "Undersokning  af  nagra  vid  Uto  Jernmalmsbrott  forekom- 

mande  Fossilier,  och  af  ett  deri  funnet  eget  Eldf ast  Alkali/'  Afh.  i  Fysik,  Kemi 
och  Min.,  6,  145-72  (1818);  "Tillagg  af  Berzelius,"  ibid.,  6,  173-6  (1818). 

(10)  ANON    "Additional  observations  on  lithium  and  selenium  by  Professor  Berze- 

lius," Annals  of  Philos.,  (1),  11,  374  (May,  1818);  THOMAS  THOMSON, 
"History  of  Physical  science  from  the  commencement  of  the  year  1817,  ima., 
(1),  12,  16  (July,  1818);  ANON.,  "An  account  of  the  new  alkali  lately  dis- 
covered in  Sweden,"  Quarterly  ].  of  Sci.  and  the  Arts,  5,  337-40  (1818); 
"Von  Petalit  und  dem  schwedischen  rothen  dichten  Feldspath  vom  Dr. 
Clarke,  Prof,  der  Mineralogie  zu  Cambridge,"  Gilbert's  Ann.  der  Physik,  59, 
241-7  (1818).  ,  ,  .  „  . 

(11 )  ARFWEDSON,  J.  A.,  "Tillagg  och  rattelser  vid  afhandlingen  om  lithion  i  Kongl. 

Vet.  Acad.  Handl.  for  Ar  1818,"  Kongl.  Vet.  Acad.  Handl,  1821,  pp.  156-9. 

(12)  BERZELIUS,  J.  J.,  "Reseanteckningar,"  P.  A.  Norstedt  &  Soner,  Stockholm,  1903, 

(13)  ARFWEDSON,  J.  A.,  "Undersokning  af  nagra  mineralier,"  Kongl.  Vet.  Acad. 

HandL,  1821,  pp.  147-55.  „ 

(14).  ARFWEDSON,  J.  A.,  "Undersokning  af  nagra  mineralier,  ibid.,  1822,  pp.  $7-^4; 
Annals  of  Philos.,  23,  343-8  (May,  1824). 

(15)  THOMSON,  THOMAS,  "History  of  Chemistry,"  Vol.   2,   Colburn  and  Bentley, 

London,  1831,  p.  229.  , 

(16)  VAUQUELTN,  N.-L.,  "Analyse  de  Taigue  marine,  ou  beril,  et  decouverte  dune 

terre  nouveUe  dans  cette  pierre,"  Ann.  chim.  phys.,  [1],  26,  155-77  (May 
(SOFloreal),  1798). 

(17)  HABER  F.  and  G.  VAN  OORDT,  "Uber  BeryDiumverbindungen,   Z.  anorg.  Lhem., 

38,  380-1,  397  (Feb.  17,  1904).  w 

(18)  ARFWEDSON,  J.  A.,  "Bidrag  tiU  en  nannare  kannedom  om  uranium,    Kongl.  Vet. 

Acad.  Handl.,  1822,  pp.  404-26;  Annals  ofPhtios.,  235  253-67  (April,  1824 )^ 

(19)  BERZELIUS    J.  J.,  "Note  sur  la  composition  des  oxides  du  platine  et  de  Tor," 

Ann.  chim.  phys.,  ( 2 ) ,  18,  149-50  ( 1821 ) .  ^ 

(20)  ARFWEDSON,  J.  A.,  "Om  svafvelsyrade  metaUsalters  sonderdelning  med  vatgas, 

Kongl  Vet.  Acad.  HandL,  1822,  pp.  427-49;  Annals  of  Philos.,  23,  329-43 
(May,  1824). 

(21 )  BROOKE   H.  J.,  "A  description  of  the  crystalline  form  of  some  new  minerals, 

Annals  of  Philos.,  21,  381-4  ( May,  1823 ) . 

(22)  SMITH   E.  F.,  "Chemistry  in  America,"  D.  Appleton  and  Co.,  New  York  and 

London,  1914,  p.  151;  HENRY  SEYBERT,  "Analyses  of  the  chrysoberyls  from 
Haddam  and  Brazil,"  Trans.  Am.  Philos.  Soc.  (N.  S.),  2,  116-23  (1825). 
Read  March  5,  1824.  „ 

(23)  WALLACH,  O.,  "Briefwechsel  zwischen  J.  Berzelius  und  F.  Wohler,     VoL  1, 

Wilhelm  Engelmann,  Leipzig,  1901,  p.  19.  Letter  of  Wohler  to  Bereelrus, 
Nov.  11,  1824. 


Courtesy  Sir  James  C.  Irvine 

Thomas  Charles  Hope,  1766-1844.     Scottish  chemist  and  physician.     Suc- 
cessor to  Dr.  Joseph  Black  at  Edinburgh.    The  first  chemist  in  Great  Britain 
to  teach  Lavoisier's  views  on  combustion.     Hope  and  Dr.  Adair  Crawford 
were  the  first  to  distinguish  between  baryta  and  strontia. 


If  matter  cannot  be  destroyed, 
The  living  mind  can  never  die; 

If  een  creative  when  alloy'd, 
How  sure  its  immortality! 


Then  think  that  intellectual  light, 
Thou  loved'st  on  earth  is  burning 
still, 

Its  lustre  purer  and  more  bright. 
Obscured  no  more  by  mortal  will 


20 

Alkaline  earth  metals,  magnesium,  cadmium 


The  isolation  of  the  alkaline  earth  metals  required  the  combined 
genius  of  Davy  and  Berzelius.  After  the  latter  and  M.  M.  af 
Pontin  had  decomposed  lime  and  baryta  by  electrolysing  a  mix- 
ture of  the  alkaline  earth  and  mercury,  Davy  was  able  in  1808  to 
prepare  the  amalgams  in  larger  quantity  and,  by  distilling  of 
the  mercury,  to  isolate  the  metals,  strontium,  barium,  calcium, 
and  magnesium.  In  the  year  1817  a  number  of  preparations  of 
zinc  oxide  sold  by  German  apothecaries  were  confiscated  by 
the  inspectors,  who  found  that  zinc  carbonate  had  been  sub- 
stituted for  the  oxide,  that  the  carbonate  became  yellow  upon 
heating,  and  that,  when  hydrogen  sulfide  was  passed  into  an 
acid  solution  of  the  carbonate,  a  yellow  precipitate  resembling 
arsenious  sulfide  was  thrown  down.  The  researches  of  Dr. 
Stromeyer,  Dr.  Roloff,  and  Mr.  Hermann  proved,  however,  that 
this  yellow  precipitate  was  not  arsenious  sulfide,  but  the  sulfide 
of  an  unknown  metal.  Thus  the  good  name  of  the  manufactur- 
ing pharmacies  was  restored,  and  the  chemical  world  was  en- 
riched by  the  discovery  of  the  new  element,  cadmium. 


CALCIUM 


A 


Llthough  the  ancients  had  many  uses  for  lime,  they  knew  noth- 
ing of  its  chemical  nature.  The  "De  Re  Rustica"  of  Marcus  Porcius  Cato 
the  Censor  (234-149  B.C.),  the  "De  Architecture"  of  Marcus  Vitruvius 
Pollio  (who  lived  in  the  reign  of  Augustus),  and  the  "Historia  Naturalis" 
of  Pliny  the  Elder  all  discuss  the  preparation,  properties,  and  uses  of  lime 
(44,  45,  46).  Vitruvius  noticed  that  lime  from  the  kiln,  though  it  was  as 
bulky  as  the  original  limestone,  had  "lost  about  one  third  of  its  weight 
owing  (he  said)  to  the  boiling  out  of  the  water"  (47).  In  1755  Dr.  Joseph 
Black  proved  that  this  loss  in  weight  is  actually  due  to  the  escape  of  "fixed 
air"  ( carbon  dioxide  gas ) .  These  experiments  were  described  in  his  paper 
entitled,  "Experiments  upon  magnesia  alba,  quick-lime,  and  some  other 
alkaline  substances"  (67). 

Although  the  word  alabaster  is  sometimes  applied  to  a  kind  of  translu- 
cent gypsum  (calcium  sulfate),  Egyptian  alabaster  was  a  form  of  calcite 

505 


506  DISCOVERY  OF  THE  ELEMENTS 

(calcium  carbonate).  Howard  Carter's  great  work  describing  the  tomb 
of  Tut-ankh-Amen  contains  a  picture  of  a  lovely  calcite  lamp  found  in  the 
tomb  (71). 

Ancient  Egyptian  and  Grecian  mortars  and  plasters  were  made  by 
heating  crude  gypsum  (calcium  sulfate  dihydrate)  until  it  became  par- 
tially dehydrated  (72).  Roman  mortars,  however,  were  prepared  by 
burning  limestone,  for  the  lime  mortar  withstood  better  the  moist  climate 
of  Italy  (73).  A.  Lucas  states  that  the  mortar  used  in  the  pyramids  at 
Gizeh  and  in  the  temples  of  Karnak  was  made  from  gypsum,  and  that  all 
the  plaster  in  Tut-ankh-Amen's  tomb  is  crude  gypsum  similar  to  that  still 
made  near  Cairo  and  Alexandria  (71). 

Theophrastus  of  Eresus  used  the  word  gypsum  to  include  both  the 
crude  mineral  and  the  product  (plaster  of  Paris)  obtained  by  partially 
dehydrating  it.  "The  Stone,"  said  he,  "from  which  Gypsum  is  made,  by 
burning,  is  like  Alabaster;  it  is  not  dug,  however,  in  such  large  Masses,  but 
in  separate  Lumps.  Its  Viscidity  and  Heat,  when  moistened,  are  very 
wonderful.  They  use  this  in  Buildings,  casing  them  with  it,  or  putting  it 
on  any  particular  Place  they  would  strengthen.  They  prepare  it  for  Use 
by  reducing  it  to  Powder  and  then  pouring  Water  on  it,  and  stirring  and 
mixing  the  Matter  well  together  with  wooden  Instruments.  For  they 
cannot  do  this  with  the  Hand  because  of  the  Heat.  They  prepare  it  in 
this  Manner  immediately  before  the  Time  of  using  it;  for  in  a  very  little 
While  after  moistening,  it  dries  and  becomes  hard,  and  not  in  a  Condition 
to  be  used.  This  Cement  is  very  strong,  and  often  remains  good  even  after 
the  Walls  it  is  laid  on  crack  and  decay.  ...  It  is  also  excellent,  and 
superior  to  all  other  Things,  for  making  Images;  for  which  it  is  greatly 
used,  and  especially  in  Greece,  because  of  its  Pliableness  and  Smoothness" 
(74). 

Dioscorides  Pedanios  said  that  calx  viva  (quicklime)  was  made  by 
heating  shells  of  "sea  fishes  called  Buccinoe"  (whelks),  pebble  stones,  or 
marble  (75). 

In  about  975  A.D.  the  Persian  pharmacist  Abu  Mansur  Muwaffaq 
wrote  his  "Book  of  Pharmacological  Principles,"  in  which  he  described 
for  the  first  time  the  use  of  the  plaster  of  Paris  bandage  for  bone  fractures 
(76). 

Soon  after  the  United  States  purchased  the  vast  region  known  as 
"Louisiana"  in  Thomas  Jefferson's  administration,  the  following  article 
on  "Gypsum  from  Upper  Louisiana"  appeared  in  S.  L.  MitchilTs  Medical 
Repository:  "Among  the  productions  of  this  newly-acquired  country  is 
to  be  reckoned  plaster  of  Paris,  Specimens  of  a  very  pure  gypsum  have 
been  brought  from  about  150  leagues  up  the  Missouri.  It  is  said  to  exist 
there  in  abundance.  This,  in  process  of  time,  will  amply  supply  that 


ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM  507 

inland  country  with  the  sulphate  of  lime  for  all  the  purposes  of  agriculture, 
architecture,  and  the  other  arts.  It  is  remarkable  how  scantily  gypsum  is 
scattered  through  Fredonia.*  Except  some  small  parcels  which  have  been 
brought  from  St  Mary's,  between  the  Patuxent  and  Potowmac  [sic]  in 
Maryland,  some  other  samples  from  the  town  of  Marcellus,  in  'Onondaga 
County,  New  York,  and  some  other  pieces  obtained  from  the  bed  of  the 
river  below  the  Falls  of  Niagara,  we  have  hitherto  seen  but  few  traces  of 
this  valuable  stone  in  the  United  States.  It  is  owing  to  the  scarcity  of 
plaster  of  Paris  within  our  territories  that  we  are  obliged  to  import  the 


Sir  Humphry  Davy,  1778-1829.  Pro- 
fessor of  chemistry  and  lecturer  at  the 
Royal  Institution,  London.  Scientist, 
poet,  and  humanitarian.  Donor  of  the 
Davy  Medal. 


From  Muspratt's  "Chemistryy  Theoretical, 
Practical  and  Analytical" 


greater  part  of  what  we  consume.  And  the  principal  portion  of  the  great 
quantity  employed  in  constructing  houses  and  manuring  lands  is  brought 
from  the  British  dominions  bordering  on  the  Bay  of  Fundy"  (77). 

George  Ernst  Stahl  (1660-1734)  thought  that  in  the  slaking  of  lime 
the  earthy  element  combined  with  the  watery  element  to  form  a  salt.  He 
admitted  that  there  are  distinct  earths  that  might  be  converted  into  metals 
by  combining  with  phlogiston.  Though  most  eighteenth-century  chemists 
thought  that  lime  and  baryta  were  elements,  Lavoisier  believed  them  to 
be  oxides  (2,  12).  "It  is  probable,"  said  he,  "that  we  know  only  part  of 
the  metallic  substances  which  exist  in  Nature;  all  those,  for  example,  that 

*  Since  it  is  impossible  to  make  an  adjective  from  the  name  United  States  of  America, 
the  Medical  Repository  proposed  and  used  the  words  Fredonia  and  Fredonian. 


508 


DISCOVERY  OF  THE  ELEMENTS 


have  more  affinity  for  oxygen  than  for  carbon  are  not  capable  of  being 
reduced  or  brought  to  the  metallic  state,  and  they  must  not  present 
themselves  to  our  eyes  except  in  the  form  of  oxides,  which  we  do  not 
distinguish  from  the  earths.  It  is  very  probable  that  baryta,  which  we 
have  just  classified  with  die  earths,  is  one  of  these;  it  presents  experi- 
mentally properties  which  closely  ally  it  with  metallic  substances.  It  is 
possible,  strictly  speaking,  that  all  the  substances  which  we  call  earths  may 
be  simply  metallic  oxides  irreducible  by  the  methods  we  employ"  (12). 


K     s 


.  D, 


p^V-l?1C^^it•i^,^V/|1^lt-^v^^v  HI",  •  . ,  ': 

[^  large  A^^%^fe%,^e  jfe^fto^e*  and  Tmpw* 
?$£jjg^  v  -; , 

'^tvffej, '" ibf  /'"r   rt^^/^V-i^i'lp^Kr/- r-<i  s '\*    i1 

^^jw*  v«». 


Title  Page  of  the  "Chemical 
Works  of  Caspar  Neumann" 
( 1683-1737).  Apothecary 
and  professor  of  chemistry  at 
Berlin.  His  writings  were 
carefully  studied  by  Scheele 
and  Davy. 


Caspar  Neumann  made  some  elaborate  but  unsuccessful  attempts  to 
obtain  a  metal  from  quicklime  (3),  but  for  this  difficult  reduction  new 
methods,  new  apparatus,  and  the  genius  of  a  Davy  were  required. 

Sir  Humphry's  ardent  nature  could  not  rest  content  with  his  recent 
triumphs  over  sodium  and  potassium.  With  a  conqueror's  enthusiasm  he 
pushed  ahead  toward  the  still  more  difficult  task  of  decomposing  the 
alkaline  earths.  In  his  first  attempts  he  passed  a  current  through  the  moist 
alkaline  earth,  which  was  protected  from  the  air  by  a  layer  of  naphtha. 
There  was  slight  decomposition,  but  any  metal  that  may  have  been  formed 
combined  immediately  with  the  iron  cathode  (3). 


ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM  509 

Davy  then  tried  to  use  potassium  directly  as  a  reducing  agent.  "I 
heated  potassium,"  said  he,  "in  contact  with  dry,  pure  lime,  barytes,  stron- 
tites,  and  magnesia,  in  tubes  of  plate  glass;  but  as  I  was  obliged  to  use 
very  small  quantities,  and  as  I  could  not  raise  the  heat  to  ignition  without 
fusing  the  glass,  I  obtained  in  this  way  no  good  results."  Although  the 
potassium  attacked  the  earth  and  the  glass,  no  distinct  metallic  globules 
were  obtained  (3). 

One  method  he  finally  adopted  was  to  mix  the  non-conducting,  dry 
earth  (lime,  strontia,  or  baryta)  with  excess  potash  and  fuse  it.  When  he 
covered  the  alkaline  mixture  with  naphtha  and  passed  an  electric  current 
through  it,  he  soon  saw  metallic  globules  rising  and  bursting  into  flame, 
but  when  the  flame  died  out,  there  remained  nothing  except  potash  and 
the  alkaline  earth  with  which  he  had  started  (2,3}. 

Although  greatly  disappointed  over  this  failure,  Sir  Humphry  soon 
thought  out  another  plan  of  attack.  This  time  he  mixed  lime  with  mer- 
curic oxide  and  obtained  a  small  amount  of  calcium  amalgam.  He  also 
made  similar  alloys  of  the  other  alkaline  earths  with  mercury,  silver,  tin, 
and  lead,  but  never  obtained  enough  of  the  alloy  to  permit  the  isolation 
of  the  alkaline  earth  metal.  In  May,  1808,  however,  Berzelius  wrote  Davy 
that  he  and  Dr.  M.  M.  af  Pontin,  the  king's  physician,  had  decomposed 
lime  by  mixing  it  with  mercury  and  electrolyzing  the  mixture,  and  that 
they  had  been  equally  successful  in  decomposing  baryta  and  preparing 
barium  amalgam  (2,  13). 

With  the  help  of  this  suggestion,  Davy  finally  worked  out  a  method 
of  obtaining  the  alkaline  earth  metals  themselves.  He  mixed  the  moist 
earth  with  one-third  its  weight  of  mercuric  oxide,  and  placed  it  on  a 
platinum  plate  connected  to  the  positive  pole  of  a  powerful  battery.  He 
then  hollowed  out  a  little  cavity  in  the  center  of  the  mixture,  and  poured 
a  globule  of  mercury  into  it  in  order  to  make  possible  the  use  of  a  heavy 
current  from  "a  battery  of  five  hundred."  A  platinum  wire  dipping  into 
the  mercury  was  connected  to  the  negative  pole.  By  this  means  Sir 
Humphry  obtained  enough  of  the  calcium  amalgam  so  that  he  could  distil 
off  the  mercury  and  see  for  the  first  time  the  rather  impure  silvery-white 
metal,  calcium  (2,3,7). 

In  his  letter  of  July  10,  1808,  Davy  acknowledged  his  indebtedness  to 
Berzelius  and  Dr.  Pontin.  After  describing  his  early  failures  he  said: 

Since  I  have  been  favoured  with  your  papers,  I  have,  however,  made 
new  and  more  successful  attempts,  and  by  combining  your  ingenious  mode  of 
operating  with  those  that  I  before  employed,  I  have  succeeded  in  obtaining 
sufficient  quantities  of  amalgams  for  distillation.  At  the  red  heat  the  quick- 
silver rises  from  the  amalgams  and  the  bases  remain  free.  The  metals  of 
strontites,  barytes,  and  magnesia  are  all  that  I  have  experimented  upon  in 
this  way;  but  I  doubt  not  the  other  earths  will  afford  similar  results.  ...  I 


510  DISCOVERY  OF  THE  ELEMENTS 

consider  this  letter  as  addressed  in  common  to  you  and  your  worthy  fellow 
labourer,  Dr.  Pontin,  to  whom  I  must  beg  you  to  present  my  compliments" 
(14). 

Pure  calcium  cannot  be  prepared  by  the  method  of  Davy  and 
Berzelius,  and  a  successful  commercial  process  was  not  perfected  until 
nearly  a  century  later  (32). 

Calcium  in  Plant  and  Animal  Nutrition.  Calcium  is  essential  to  plant 
and  animal' life  and  is  present  in  adequate  amounts  in  many  soils  (78). 
The  outer  green  leaves  of  cabbages  and  certain  other  leafy  vegetables  con- 
tain much  more  calicum  than  the  inner  white  ones  (79,  80,  81 ) .  Large 
amounts  of  it  are  present  in  the  human  body.  The  composition  of  bone 
suggests  that  it  must  be  closely  related  to  the  apatite  series  of  minerals, 
which  have  the  formula  nCa3(PO4)2-CaCO3,  in  which  n  has  a  value 


Dr.    Pontin    (M.    M.    af    Pontin),    1781-1858, 

Physician  to  the  King  of  Sweden.  He  collabo- 
rated with  Berzelius  in  preparing  amalgams  of 
calcium  and  barium  by  electrolyzing  lime  or 
baryta  in  presence  of  mercury.  Author  of  a 
biography  of  Berzelius. 


between  2  and  3,  and  fluorine,  hydroxyl,  etc.  may  replace  the  carbonate 
radical.  X-ray  analyses  by  H.  H.  Roseberry,  A.  B.  Hastings,  and  J.  K. 
Morse  show  that  bone  salts  most  closely  resemble  the  rare  mineral  dahlite 
(82,  83).  Although  most  of  the  calcium  in  the  body  is  located  in  the 
skeleton  and  teeth,  that  present  in  the  blood  and  tissues  is  of  great 
physiological  importance  ( 82 ) . 

BARIUM 

Early  in  the  seventeenth  century  Vincenzo  Casciarolo,  a  shoemaker 
and  alchemist  in  Bologna,  noticed  that  when  heavy  spar  is  mixed  with  a 
combustible  substance  and  heated  to  redness,  the  resulting  mixture,  which 
became  known  as  the  "Bologna  stone/'  emits  a  phosphorescent  glow. 


ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM  511 

Casciarolo  communicated  his  discovery  to  Giovanni  Antonio  Magini,  a 
mathematician  in  Bologna  (56).  In  a  scholarly  article  on  the  history  of 
this  substance,  A.  Bernardi  quoted  from  the  volume  "Phosphorus,  or  the 
Bolognian  stone  prepared  to  shine  again  in  the  dark/'  which  Marco 
Antonio  Celli  had  published  in  1680  ( 56 ) .  According  to  Celli,  Casciarolo 
carried  home  some  shining  pebbles  he  had  found  on  a  sterile  slope  of 
Mount  Paterno,  experimented  with  them  (perhaps  to  see  whether  they 
had  any  occult  virtues),  and  noticed  that  after  they  had  been  heated  in  a 
certain  way  and  exposed  to  the  sun,  they  became  luminous  even  in  the 
dark.  Celli  suggested  that  Casciarolo  may  have  been  deceived  both  by 
the  high  specific  gravity  and  by  the  sulfur  content  of  the  mineral  into 
considering  it  a  suitable  substance  for  transmutation  into  gold  ( 56 ) .  Some 
of  the  earliest  descriptions  of  this  "Bologna  stone"  and  the  "Bolognian 
phosphorus"  prepared  from  it  were  written  by  J.  C.  La  Galla  (1612), 
P.  Poterius  (Potier)  (1622),  Ovidio  Montalbanus  (1634),  A.  Kircher 
(1641-),  Nicolas  Lemery  (1697),  and  L.  F.  Marsigli  (1698)  (84).  The 
Aristotelian  philosopher  Fortunio  Liceto  (Licetus)  maintained  in  1640 
that  the  phosphorescence  of  the  Bologna  stone  could  be  compared  to  the 
secondary  light  of  the  moon,  a  hypothesis  which  the  aged  Galileo  effect- 
ively contested  in  the  last  of  his  many  scientific  contributions  (85). 

W.  Derham  in  1726  gave  the  following  account  of  the  "Bolognian 
phosphorus":  "The  stone  is  found  in  three  Places  near  the  City  of 
Bologna;  the  first  is  called  Pradalbino;  the  second  is  a  small  Brook  near  the 
Village  Roncaria;  the  third  is  called  Monte  Paterae-,  and  is  most  noted  for 
these  Stones;  .  .  ..  It's  known  by  a  Glittering  .  .  .  which  surprizes  the  eye. 
It  was  first  found  out  by  ...  Vincenzo  Casciarolo,  a  Cobler,  but 
ingenious,  and  a  Lover  of  Chymistry;  who,  trying  several  Experiments 
with  these  Stones,  by  Chance  happened  on  this  Way  of  preparing  them, 
so  as  to  make  them  shine  in  the  Dark,  after  they  had  been  some  Time 
exposed  to  the  Sun.  .  .  .  It's  usually  no  bigger  than  an  Orange;  and 
tho'  Licetus  affirms,  there  never  was  any  greater  than  that  in  Androvandus' 
[Ulisse  Aldrovandfs]  Museum,  weighing  about  two  Pound  and  a  half; 
yet  the  Author  hath  had  of  five  Pound.  It's  very  heavy,  considering  the 
Bulk,  as  being  probably  compounded  of  several  mineral  Substances.  .  .  . 
When  It's  well  prepared,  it  leaves  a  Lustre  in  the  Superficies,  and  is 
enlightened,  not  only  by  the  Sun,  but  the  Moon,  and  a  Fire;  but  by  these 
not  so  strongly,  as  the  Sun.  The  Light,  tho'  it  appear  like  a  Coal,  yet  is 
not  sufficient  to  read  with,  unless  applied  close  to  the  Word.  It  will  not 
retain  the  Light  very  long,  at  one  Time,  nor  its  Vertue  above  five  or  six 
Years  .  .  ."  (37).  Derham  also  described  in  great  detail  the  method  of 
preparing  the  "Bolognian  phosphorus"  from  the  mineral. 

Ulisse  Aldrovandi  had  a  large  specimen  of  this  mineral  in  his  museum. 
He  was  born  in  Bologna  in  1522  of  noble  parentage.  To  satisfy  his  boyish 


512 


DISCOVERY  OF  THE  ELEMENTS 


curiosity,  he  made  long  secret  journeys,  often  on  foot  In  his  studies  at 
Bologna  and  Padua  he  showed  intense  interest  in  every  branch  of  science 
and  in  Roman  antiquities.  He  received  his  doctorate  in  natural  history 
in  Bologna  in  1553  and  later  became  a  professor  of  pharmacognosy  there. 
Aldrovandi  founded  a  great  botanical  garden  and  museum  where  he 
exhibited  rare  and  valuable  natural  productions  from  all  parts  of  the  world. 
In  this  costly  undertaking  he  was  aided  by  the  Senate  and  philanthropic 
Italian  princes.  The  museum  with  its  rich  library  was  located  in  his  own 
home.  His  descriptions  of  the  specimens  were  published  during  his  life- 
time in  four  folio  volumes.  Other  volumes  for  which  he  had  collected 


Ulisse  Aldrovandi  (or  Aldrovandus ) , 
1522-1605  (?).  Italian  scholar  and  col- 
lector, well  versed  in  all  branches  of  nat- 
ural science.  Professor  of  pharmacognosy 
at  Bologna.  Founder  of  a  great  botani- 
cal garden,  museum,  and  library,  which 
he  bequeathed  to  the  state.  Volume  4  of 
the  superbly  illustrated  1642  folio  edition 
of  his  complete  works  contains  an  account 
of  the  "Bologna  stone,"  barite  (De 
lapide  illvrninabili. ) 


Naturalist's  Library,  vol.  7 


the  data  were  published  after  his  death  by  other  scholars.  After  forty- 
eight  years  of  teaching,  Aldrovandi  was  pensioned.  He  died  in  1605  at 
the  age  of  eighty-three  years  and  bequeathed  his  great  collections  and 
library  to  the  state  (86).  The  superbly  illustrated  1642  edition  of  his 
complete  works  contains  an  account  of  the  Bologna  stone  (de  lapide 
iUvminabiH)  (57). 

Father  Athanasius  Kircher  said  that  the  "phosphorus"  was  made  by 
pulverizing  the  Bologna  stone,  mixing  it  with  white  of  egg  or  linseed  oil, 
and  calcining  it  in  a  special  furnace.  He  found  specimens  in  the  alum 
mines  at  Tolfa  (59).  Biographical  sketches  of  Father  Kircher  were  pub- 
lished in  The  Hormone  in  1934  (109)  and  in  the  Journal  of  Chemical 
Education  in  1955  (139). 

Nicolas  Lemery  stated  in  his  "Cours  de  Chyrnie"  that  "this  Stone  is 
bituminous,  and  full  of  Sulphur,  which  is  the  thing  that  gives  it  this  dis- 


ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM  513 

position  to  shine  in  the  dark.  .  .  .  When  it  has  not  been  calcined  enough, 
it  yields  no  light  at  all,  because  the  sulphureous  parts  have  not  been  put 
into  sufficient  motion,  and  when  it  is  calcined  too  much,  these  sulphureous 
parts  are  thereby  lost"  (88). 

A  seventeenth-century  item  in  the  Philosophical  Transactions  states 
that  "Though  several  Persons  have  pretended  to  know  the  Art  of  Preparing 
and  Calcining  the  Bononian  Stone,  for  keeping  a  while  the  Light  once 
Imbibed,  yet  there  hath  been  indeed  but  One  who  had  the  true  Secret 
of  performing  it.  This  was  an  Ecclesiastick,  who  is  now  dead,  without 
having  left  that  Skill  of  his  to  any  one.  .  .  .  S.  [Marcello]  Malpighi  takes 
notice,  That  one  S.  Zagonius  had  a  way  of  making  out  of  the  Bononian 
Stone  Calcin  d,  Statues  and  Pictures  variously  Shining  in  the  Dark.  But 
he  adds  (to  our  sorrow)  that  that  Person  lately  Dy'd,  without  discovering 
to  any  Body  his  Method  of  Preparing  it"  (58).  In  his  "History  ...  of 
Vision,  Light,  and  Colours,"  Joseph  Priestley  stated  that  "the  best  method 
of  preparing  the  Bolognian  stone  had  been  kept  a  secret  in  the  Zagonian 
family,  all  of  whom  had  died  without  revealing  it"  ( 59 ) . 

Willem  Homberg  observed  that  Balduin's  phosphorus  (anhydrous 
calcium  nitrate)  was  similiar  to  the  Bolognian  but  shone  with  a  somewhat 
feebler  light.  B.-B.  de  Fontenelle's  eulogy  states  that  Homberg  "worked 
at  Bologna  on  the  stone  which  bears  the  name  of  that  city,  and  restored 
to  it  all  its  light,  for  the  secret  of  it  had  almost  been  lost"  (55).  When 
he  repeated  the  experiment  in  Paris,  he  was  unsuccessful.  Homberg  him- 
self finally  found  that  when  he  ground  the  materials  in  an  iron  mortar,  the 
experiment  failed,  but  when  he  used  a  bronze  mortar  and  pestle,  he 
obtained  a  luminous  product  (56).  Some  impurities  serve  as  activators 
for  producing  a  high  degree  of  fluorescence,  whereas  others  have  an 
inhibiting  effect.  Hence  in  the  most  modern  plants  for  the  manufacture 
of  fluorescent  lamps,  dust  must  be  completely  excluded  (57). 

Homberg  performed  some  of  these  experiments  in  the  presence  of 
his  friend  Nicolas  L&nery.  According  to  Lemery,  the  Bologna  stone  was 
found  "in  several  places  in  Italy,  as  near  the  City  of  Roncaria,  at  Pradal- 
bino,  at  the  foot  of  Mt.  Paterno,  which  is  part  of  the  Alps  and  about  one 
French  league  from  the  City  of  Bologna.  Father  Kirker  [Kircher],  in 
his  book  "de  Magnate,"  said  that  he  found  them  near  the  rock  alum  pit 
at  Tolfa,  but  the  greatest  quantity  and  the  best  ones  come  from  Mt. 
Paterno"  (88). 

The  Abbe  Jean-Antoine  Nollet,  in  his  "Legons  de  physique  experi- 
mentale,"  mentioned  the  cold  light  of  the  Bologna  stone  and  the  sul- 
phurous odor  which  the  flame  imparted  to  it.  "The  odor  that  the  Bologna 
stone  acquires  on  passing  through  the  flame,"  said  he,  "gives  sufficient 
evidence  that  these  natural  sulphurs  have  been  liberated  from  the  terres- 


514  DISCOVERY  OF  THE  ELEMENTS 

trial  part  and  from  the  other  principles  so  that  they  are  able  to  pass 
easily  from  the  interior  to  the  outside:  these  refined  sulphurs,  like  all 
the  rest,  contain  particles  of  fire,  but  with  this  difference:  that  being 
strongly  disposed  to  obey  the  expansive  force  of  that  element,  the  merest 
trifle  inflames  them;  even  the  faintest  daylight  gives  sufficient  fire  to 
illumine  them.  It  is  perhaps  also  by  a  slow  dissipation  of  these  inflam- 
mable parts  from  its  surface  that  the  stone  gradually  loses  its  quality; 
one  can  at  least  suppose  so,  since  it  can  be  kept  longer  when  wrapped 
in  cotton  .  .  .  and  is  restored  by  a  new  calcination,  as  if  the  action  of 
the  fire  brought  new  sulphurs  to  the  surface"  (89). 

Priestley  mentioned  that  Jacopo  Bartolomeo  Beccari  and  other  scien- 
tists of  Bologna  in  1711  "took  a  great  deal  of  pains  with  the  chymical 
analysis  of  this  fossil,  by  which  they  thought  they  discovered  in  it  some 
sulphur  and  also  an  alkaline  salt"  (59).  Before  testing  his  phosphors, 
Beccari  used  to  remain  for  some  time  in  a  dark,  portable  booth,  or  cell. 
When  the  pupils  of  his  eyes  had  become  sufficiently  dilated,  he  was  able 
to  observe  the  dim,  cold  light  which  the  phosphorescent  substances 
emitted  (59). 

Beccari  was  born  in  Bologna  in  1682.  After  teaching  medicine  at 
the  University  of  Bologna  for  nearly  a  quarter  of  a  century,  he  became  in 
1737  its  first  professor  of  chemistry-the  first,  in  fact,  in  all  Italy.  After 
forty  years  of  service  to  the  University,  he  was  pensioned,  but  neverthe- 
less continued  his  work  there  for  several  years  more.  He  died  in  Bologna 
in  1766  at  the  age  of  eighty-three  years  (90,  138). 

J.  G.  Wallerius  regarded  heavy  spar  as  a  kind  of  gypsum  (91),  but 
Cronstedt  classified  it  as  a  special  species.  In  1750  A.  S.  Marggraf  proved 
it  to  be  a  sulfate,  and  he  too  believed  the  base  of  it  to  be  lime  (92,  93). 

J.  W.  von  Goethe  collected  specimens  of  the  Bologna  stone  at  Paterno 
in  1786,  took  them  back  to  Weimar,  made  many  experiments  with  them, 
and  in  1792  discovered  that  only  the  violet  end  of  the  spectrum  caused 
the  phosphorescence.  Goethe  said  that  in  Bologna  the  little  phospho- 
rescent cakes  prepared  from  the  Bologna  stone  were  called  "fosfori"  (94). 
The  modern  name  of  the  Bologna  stone  is  barite,  barium  sulfate. 

In  his  famous  investigation  of  pyrolusite,  which  was  published  in 
1774,  C.  W.  Scheele  discovered  a  new  base,  baryta,  which  gave  a  white, 
nearly  insoluble  precipitate  with  sulfuric  acid  and  with  vitriols  (15,  18). 
Although  he  first  encountered  the  new  alkali  merely  as  an  accidental  or 
nonessential  constituent  of  pyrolusite,  he  soon  received  from  Torbern 
Bergman  a  specimen  of  this  mineral  to  which  some  peculiar  crystals  were 
attached.  On  February  28,  1774,  Scheele  wrote  to  J.  G.  Gahn,  "Haven't 
you  seen,  Sir,  on  Braunstein,  especially  on  some  of  it,  a  few  white  sparry 
crystals?  You  undoubtedly  have.  One  might  take  it  for  gypsum  or  cal- 


ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM  515 

cite,  but  incorrectly.  It  is  the  new  earth  itself,  combined  with  sulfuric 
acid.  I'm  curious  to  know  with  what  kind  of  a  name  Herr  Professor 
Bergman  will  christen  this  earth.  He  thinks  that  there  must  be  rocks 
which  contain  a  great  deal  of  this  earth"  (60).  A  month  later,  Scheele 
sent  some  of  these  crystals  to  Gahn,  who  found  that  they  had  the  same 
composition  as  massive  heavy  spar,  or  Bologna  stone. 

Although  baryta  was  at  first  a  great  rarity,  Gahn's  discovery  of  the 
composition  of  Bologna  stone  opened  up  to  chemists  an  abundant  source 
of  it.  In  his  letter  of  May  16, 1774,  Scheele  congratulated  Gahn  as  follows: 
"I  am  delighted  that  you  have  discovered  the  presence  in  heavy  spar  of 
the  earth  I  mentioned.  It  must  therefore  be  named  Schwerspatherde 
(earth  of  heavy  spar).  Scarcely  had  I  investigated  the  crystals  you  sent 
me  until  I  hurried  to  Herr  Professor  Bergman  and  received  from  him  a 
piece  of  this  spar,  on  which  I  immediately  began  to  experiment"  (60). 

Baryta  was  first  distinguished  from  lime  in  1779  by  Scheele,  who 
prepared  it  from  heavy  spar,  a  naturally  occurring  barium  sulfate.  He 
reduced  the  sulfate  to  the  sulfide  by  heating  a  sticky,  pasty  mixture  of 
heavy  spar,  powdered  charcoal,  and  honey.  After  decomposing  the 
barium  sulfide  with  hydrochloric  acid,  he  added  excess  potassium  car- 
bonate to  precipitate  the  barium  as  the  carbonate  (15). 

Witherite.  Torbern  Bergman  predicted  that  baryta  would  also  be 
found  in  nature  combined  with  fixed  air  (carbon  dioxide),  and  in  1784 
Dr.  William  Withering  discovered  in  the  collection  of  Matthew  Boulton 
the  natural  barium  carbonate  which  is  now  known  as  witherite  (84). 
Dr.  Withering  ( 1741-1799 )  was  a  British  physician,  botanist,  and  mineral- 
ogist. He  was  a  member  of  the  Society  for  Promoting  the  Abolition  of 
the  Slave  Trade  and  of  the  famous  Lunar  Society,  in  which  he  was  closely 
associated  with  Joseph  Priestley,  Matthew  Boulton,  and  James  Watt.  At 
one  of  their  meetings  Dr.  Withering  read  an  original  humorous  poem 
entitled  "The  Life  and  Death  of  Phlogiston"  (95). 

In  1783  he  published  an  annotated  translation  of  Torbern  Bergman's 
"Sciagraphia  regni  mineralis,"  and  in  the  following  year  he  communi- 
cated to  the  Philosophical  Transactions  his  "Experiments  and  observations 
on  terra  ponderosa"  (barium  carbonate,  or  witherite)  (96).  He  stated 
that  the  specimen  he  examined  carne  from  a  lead  mine  at  Alston  Moor, 
on  the  Pennines  of  Cumberland.  Although  he  at  first  mistook  it  for  heavy 
spar  (barite)  he  soon  found  it  to  be  a  compound  of  heavy  earth  (barium 
oxide)  and  fixed  air  (carbon  dioxide)  (97). 

Commenting  on  this  discovery,  A.-F.  de  Fourcroy  said  that  "Barytes 
is  less  copious  than  either  of  the  other  two  salino-terreous  substances 
(lime  or  magnesia),  but  it  is  probably  more  copious  than  it  is  thought  to 
be.  Formerly  it  was  not  known  to  exist  in  any  body  but  barytic  sulfate  or 
ponderous  spar"  (98). 


516  DISCOVERY  OF  THE  ELEMENTS 

In  1790  James  Watt  published  a  map  of  a  lead  mine  at  Anglezark, 
Lancashire,  in  which  the  "aerated  barytes"  ( witherite )  is  found.  Since 
Watt  believed  that  Dr.  Withering  must  have  been  mistaken  as  to  the 
source  of  his  first  specimen  of  this  mineral,  many  mineralogists  regard 
Anglezark  rather  than  Alston  Moor  as  the  place  of  its  discovery  (99). 

In  1785  Dr.  Withering  introduced  the  use  of  digitalis  (foxglove)  as 
a  specific  remedy  for  dropsy  (100).  During  the  Birmingham  riots  of 
July,  1791,  in  which  Joseph  Priestley's  house  was  sacked,  Dr.  Withering 
too  was  forced  to  take  flight,  carrying  his  books  and  specimens  in  wagons 
loaded  with  hay.  Dr.  Withering's  house,  however,  was  not  destroyed 
(101).  Priestley  wrote  him  in  1792,  "One  of  the  things  that  I  regret  most 
in  being  expelled  from  Birmingham  is  the  loss  of  your  company  and  that 
of  the  rest  of  the  Lunar  Society"  (95). 

Flame  Tests.  In  1821  Nils  Nordenskiold  wrote  to  Berzelius,  "I  have 
sometimes  thought  that  I  noticed  that  fossils  containing  lithia,  when 
strongly  heated  alone,  give  the  flame  a  crimson  color;  could  that  observa- 
tion be  something  other  than  my  imagination?  Dobereiner  in  Jena  said 
that  some  chemist  from  Prague  found  that  baryta  gives  the  flame  a  green 
color;  this  I  have  not  yet  tried"  (102).  Thomas  Charles  Hope  had 
already  observed  this  green  color  in  1793  (48).  The  red  color  of  lithium, 
as  we  have  seen,  was  first  observed  by  C.  G.  Gmelin  in  1818  (103). 

Metallic  Barium.  Because  of  the  high  specific  gravity  of  baryta  and 
its  salts,  Torbern  Bergman  believed  that  it  must  be  a  metallic  oxide  (98). 
A.-L.  Lavoisier  also  expressed  the  same  view  (12).  Bertrand  Pelletier's 
attempts  to  isolate  the  metal  were  cut  short  by  his  fatal  illness.  Bidding 
farewell  to  his  friend  D.-G.-S.-T.  Gratet  de  Dolomieu,  he  said,  "I  am 
already  convinced  that  this  earth  is  of  a  metallic  nature,  although  my 
experiments  have  not  yet  led  to  the  complete  reduction  of  it;  but,  if  my 
illness  had  not  made  me  aware  that  I  can  never  resume  my  research,  I 
would  certainly  have  succeeded;  if  I  cannot  accomplish  it,  make  known 
what  I  am  now  confiding  to  you,  and  challenge  chemists  to  undertake  this 
reduction;  it  requires  special  means,  but  is  no  longer  subject  to  doubt" 
(104).  Pelletier  died  in  1797,  and  the  "special  means"  with  which  barium 
was  finally  isolated  was  the  voltaic  pile  which  Alessandro  Volta  invented 
only  three  years  later.  Sir  Humphry  Davy  first  prepared  this  metal  in 
1808  (2,3,4). 

Although  the  mineral  (barite)  in  which  this  element  was  first  recog- 
nized has  a  high  specific  gravity,  the  metal  itself  is  very  light.  Edward 
Daniel  Clarke  objected  therefore  to  the  inappropriate  name  barium 
(meaning  heavy)  for  this  metal  (105).  The  name  persists  nevertheless. 

Barium  in  Plants  and  Animals.  As  early  as  1771-72  Scheele  dis- 
covered the  presence  of  barium  in  plants.  In  his  laboratory  notes  for  his 
first  years  in  Upsala  (1771-72),  he  wrote:  "The  special  earth  which 


ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM  517 

comes  from  magn.  nigra  et  acidis  per  praecipitationem  cum  oleo  vitrioli 
must  be  present  in  plants,  for  vegetable  ash,  well  extracted  with  water  so 
that  all  tartarus  vitriolatus  is  removed,  when  dissolved  in  acido  nitri  et 
sails,  gives  with  acido  vitrioli  such  a  precipitate"  (60).  A.  E.  Nor- 
denskiold,  the  editor  of  Scheele's  notes,  regarded  this  as  strong  indication 
that  Scheele's  investigation  of  pyrolusite  must  have  been  carried  out  in 
the  years  1771-72.  In  a  letter  to  J.  G.  Gahn,  Scheele  wrote:  "I  have 
also  discovered  some  of  this  earth  [baryta]  as  well  as  a  little  Braunstein 
[manganese  dioxide]  in  vegetable  ash"  (60).  In  1776  Scheele  introduced 
the  use  of  barium  nitrate  as  a  precipitant  for  oxalic  acid  and  as  an 
indispensable  reagent  in  analytical  chemistry  (60).  Barium  chloride 
however  has  been  found  preferable  to  the  nitrate. 

J.  G.  Forchhammer  found  in  1865  that  "Baryta  occurs  both  in  sea- 
weeds and  in  sea  animals,  but  the  ashes  of  seaweeds  contain  more  of  it 
than  the  corals  and  shells.  It  can  even  be  determined  directly  in  sea 
water  and  in  the  deposits  of  the  boilers  of  the  Transatlantic  steamers" 
(106). 

In  1909-10  Professor  E,  H.  S.  Bailey  and  Dean  L.  E.  Sayre  of  the 
University  of  Kansas  detected  barium  in  the  ash  and  extract  of  elder, 
ragweed,  agrimony,  and  certain  other  Kansas  weeds  (107 y  108).  It  is 
also  present  in  minute  amounts  in  many  edible  plants  (107). 

STRONTIUM 

In  about  1787  a  rare  mineral,  which  had  long  been  exhibited  in  one 
or  two  collections,  was  brought  to  Edinburgh  in  considerable  quantity 
by  a  dealer  in  minerals.  Although  some  mineralogists  mistook  it  for 
fluorite,  most  of  them  regarded  it  as  a  kind  of  "aerated  barytes"  ( witherite, 
or  barium  carbonate).  It  was  found  in  the  lead  mine  at  Strontian, 
Argyleshire,  intermingled  with  the  lead  ore  and  with  "calcareous  and 
ponderous  spars"  (calcite  and  witherite)  (48). 

In  1790  Dr.  Ada|r  Crawford  (1748-1795)  published  a  paper  on  "The 
medicinal  properties  of  the  muriated  barytes"  (barium  chloride)  (18). 
"The  miniated  barytes  exhibited  in  St.  Thomas's  Hospital  since  the  month 
of  May,  1789,"  said  he,  "was  obtained  by  the  decomposition  of  the  heavy 
spar.  Having  procured  some  specimens  of  a  mineral  which  is  sold  at 
Strontean  [sic],  in  Scotland  under  the  denomination  of  aerated  barytes,  I 
was  in  hopes  that  the  salt  might  be  formed  with  less  difficulty  by  immedi- 
ately dissolving  that  substance  in  the  muriatic  acid.  It  appears,  however, 
from  the  following  facts,  which  have  been  verified  by  the  experiments  of 
my  assistant,  Mr.  Cruikshank,  as  well  as  by  my  own,  that  this  mineral 
really  possesses  different  properties  from  the  terra  ponderosa  [baryta]  of 
Scheele  and  Bergman"  (49). 


518  DISCOVERY  OF  THE  ELEMENTS 

Dr.  Crawford  showed  in  this  paper  that  the  salt  (strontium  chloride) 
obtained  by  dissolving  the  new  mineral  in  hydrochloric  acid  differs  in 
several  respects  from  barium  chloride.  It  is  much  more  soluble  in  hot 
water  than  in  cold,  the  strontium  salt  is  much  the  more  soluble  in  water 
and  produces  a  greater  cooling  effect,  and  these  two  chlorides  have 
different  crystalline  forms.  He  concluded  therefore  that  "the  mineral 
which  is  sold  at  Strontean  [sic]  for  aerated  terra  ponderosa  possesses 
different  qualities  from  that  earth,  although  at  the  same  time  it  must  be 
admitted  that  in  many  particulars  they  have  a  very  near  resemblance  to 
each  other/'  He  also  stated  that  "it  is  probable  that  the  Scotch  mineral 
is  a  new  species  of  earth  which  has  not  hitherto  been  sufficiently  examined" 
and  that  "Mr.  Babington  ...  has  for  some  time  entertained  a  suspicion 
that  the  Scotch  mineral  is  not  the  true  aerated  terra  ponderosa."  In  1790 
Dr.  Crawford  sent  a  specimen  of  the  new  mineral  ( strontianite,  strontium 
carbonate)  to  Richard  Kirwan  for  analysis  (50,  66). 

Adair  Crawford  was  born  at  Antrim,  Ireland,  and  received  his  degree 
of  doctor  of  medicine  at  Glasgow  in  1780.  After  settling  in  London  he 
became  a  physician  at  St.  Thomas's  Hospital,  a  member  of  the  Royal 
College  of  Physicians,  and  professor  of  chemistry  at  Woolwich.  He  died 
in  1795  at  the  estate  of  the  Marquis  of  Lansdowne,  near  Lymington, 
Hants  (51). 

According  to  Robert  Hunt,  Dr.  Crawford  "was  distinguished  by  his 
desire  to  be  accurate  in  all  his  investigations.  All  his  pieces  of  apparatus 
were  graduated  with  delicate  minuteness  which  has  never  been  surpassed" 
(52).  In  his  epitaph  for  Dr.  Crawford,  Mr.  Gilbert  Wakefield  described 
him  as  follows:  "In  the  practice  of  his  profession  intelligent,  liberal,  and 
humane;  in  his  manner  gentle,  diffident,  and  unassuming;  his  unaffected 
deference  to  the  wants  of  others,  his  modest  estimate  of  himself,  the 
infant  simplictiy  of  his  demeanor,  the  pure  emanation  of  kind  affection 
and  a  blameless  heart  rendered  him  universally  beloved.  To  these  virtues 
of  the  man  his  contemporaries  alone  can  testify.  As  a  votary  of  science 
and  author  of  a  treatise  on  Animal  Heat,  posterity  will  repeat  his  praise" 
(51). 

Near  the  close  of  1791,  Thomas  Charles  Hope  of  Edinburgh  began 
an  elaborate  investigation  of  the  Strontian  spar,  the  results  of  which  he 
presented  to  the  College  Literary  Society  of  Edinburgh  in  March,  1792, 
and  to  the  Royal  Society  of  Edinburgh  on  November  4,  1793.  In  these 
experiments  he  made  a  clear  distinction  between  witherite  and  strontian 
spar  (strontianite)  and  proved  conclusively  that  the  latter  contains  a 
new  earth  "strontites,"  or  strontia  (26,  30,  48).  He  noticed  that  strontia 
slakes  even  more  avidly  with  water  than  does  lime;  that,  like  baryta,  it 
is  much  more  soluble  in  hot  water  than  in  cold;  that  its  solubility  in  water 
is  extremely  great;  and  that  all  its  compounds,  especially  the  chloride, 


ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM  519 

tinge  the  flame  of  a  candle  red.  "This  flame  color,"  said  Hope,  "was  first 
mentioned  to  me  in  the  year  1787  by  an  ingenious  gentleman,  Mr.  Ash, 
who  was  then  studying  physic  at  Edinburgh."  Dr.  Hope  also  noticed  the 
green  flame  color  of  barium  and  the  red  of  calcium,  which  he  was  able 
to  distinguish  from  the  more  brilliant  red  of  strontium. 

Although  many  of  the  properties  of  strontia  are  intermediate  between 
those  of  lime  and  baryta,  he  proved  that  it  is  not  a  combination  of  the  two 
and  that  it  "bears  repeated  solutions,  crystallizations,  and  precipitations 
without  showing  the  smallest  disposition  to  a  separation  of  principles" 
(48).  Thus  it  is  evident  that  Dr.  Hope  foreshadowed  in  1793  one  of 
the  triads  which  J.  W.  Dobereiner  pointed  out  in  1829. 


Benjamin  Silliman  the  Elder, 
1778-1864.  American  chem- 
ist, geologist,  mineralogist, 
and  pharmacist.  This  minia- 
ture by  Rogers  was  made  in 
1818,  the  year  in  which  Sil- 
liman founded  the  American 
Journal  of  Science  (thirteen 
years  after  he  had  studied 
in  Edinburgh  under  T.  C. 
Hope). 


Benjamin  Silliman  the  Elder  studied  at  Edinburgh  in  1805.  "My 
earliest  introduction/'  said  he?  "among  men  of  science  was  to  Dr.  Thomas 
Hope,  Professor  of  Chemistry  &c.  in  the  University  of  Edinburgh.  I  found 
him  at  his  house  in  New  Town  and  received  a  very  kind  and  courteous 
welcome.  Dr.  Hope  was  a  polished  gentleman,  but  a  little  stately  and 
formal  withal.  ...  He  proved  himself  a  model  professor  and  fully 
entitled  to  act  as  a  mentor.  The  professorship  of  chemistry  was,  at  the 
time  of  my  Edinburgh  residence,  very  lucrative.  The  chair  was  so  ably 
filled  and  the  science  so  fully  illustrated  by  experiments  that  the  course 


520 


DISCOVERY  OF  THE  ELEMENTS 


drew  a  large  audience  which,  at  three  guineas  a  ticket,  probably  gave 
him  an  income  of  four  thousand  dollars  or  more-some  said,  five  thousand. 
He  with  his  brother  kept  bachelors'  hall  in  a  handsome  house  on  Princes 
Street,  in  the  New  Town.  .  .  . 

"Dr.  Hope's  lectures  .  .  .  were  not  only  learned,  posting  up  the 
history  of  the  discovery,  and  giving  the  facts  clearly  and  fully,  but  the 
experiments  were  prepared  on  a  liberal  scale.  They  were  apposite  and 
beautiful,  and  so  neatly  and  skilfully  performed  that  rarely  was  even  a 
drop  spilled  upon  the  table.  ...  Dr.  Hope  lectured  in  full  dress,  with- 
out any  protection  for  his  clothes;  he  held  a  white  handkerchief  in  his 
hand,  and  performed  all  his  experiments  upon  a  high  table,  himself 
standing  on  an  elevated  platform,  and  surrounded  on  all  sides  and  behind 
by  his  pupils.  .  ."  (53). 


Richard  Kirwan,  1733-1812.  Irish  chem- 
ist. Author  of  a  treatise  on  water  anal- 
yses, which  is  one  of  the  first  books  on 
quantitative  analysis.  Famous  for  his 
early  researches  on  strontia. 


In  his  "Story  of  the  University  of  Edinburgh,"  Sir  Alexander  Grant 
said  that  "Hope  was  fully  alive  to  the  importance  of  the  quantitative  age 
in  Chemistry  ...  he  had  learnt  Lavoisier's  views  from  himself,  and  in 
personal  communication  with  Dalton  had  imbibed  his  ideas  of  atomic 
constitution."  Professor  Hope's  two  greatest  contributions  to  science  were 
his  research  on  strontia  and  his  observation  of  the  curious  and  beneficent 
property  that  water  has  of  attaining  its  maximum  density  at  a  certain 
temperature  (now  fixed  accurately  at  4°C.).  He  abandoned  research, 
however,  in  order  to  devote  all  his  time  to  the  improvement  of  his  lectures. 


ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM  521 

Since  he  sometimes  had  more  than  five  hundred  students,  it  was  necessary 
for  him  to  perform  the  lecture  experiments  on  a  very  large  scale  (54). 

Among  the  first  to  investigate  strontia  were  F.  G.  Sulzer,  J.  F.  Blumen- 
bach,  J.  G.  Schmeisser  (18),  Court- Apothecary  J.  K.  F.  Meyer  of  Stettin, 
R.  Kirwan  (28,  29,  50),  M.  H.  Klaproth  (19),  Bertrand  Pelletier  (16), 
Tobias  Lowitz  (64),  and  Fourcroy  and  Vauquelin  (17).  In  1799  George 
Smith  Gibbes  of  Bath  analyzed  a  crystalline  stone  from  the  neighborhood 
of  Sodbury,  Gloucestershire,  where  it  was  used  for  making  gravel  walks, 
and  found  it  to  be  strontium  sulfate  (celestite)  (110). 

Sir  Humphry  Davy  isolated  the  metal  in  1808  by  the  method  he  had 
used  for  calcium  and  barium  (5,  3).  In  1924  P.  S.  Danner  of  the  Uni- 
versity of  California  allowed  the  oxides  of  barium  and  strontium  to  react 
with  magnesium  or  aluminum  and,  upon  distilling,  obtained  both  barium 
and  strontium  in  a  high  state  of  purity.  His  method  was  a  refinement  of 
the  one  previously  used  by  A.  Guntz  ( 33,  34 ) . 

Strontium  in  Plants  and  Animals.  In  1812  Professor  Giuseppe  Moretti 
of  Milan  stated  that  strontium  sulfate  (celestite)  is  found  in  lavas  and 
volcanic  conglomerates,  in  conchiferous  rock,  and  in  certain  madreporites 
(111).  In  1865  J.  G.  Forchhammer  detected  strontium  in  the  boiler  scale 
of  Transatlantic  steamers  and  in  fucoid  plants,  especially  in  Fucus  vesi- 
culosus  (106).  In  1927  A.  Desgrez  and  J.  Meunier  detected  strontium 
carbonate  in  human  bones  and  teeth  (112,  113,  114).  Since  radio- 
strontium,  like  radiocalcium,  has  a  tendency  to  deposit  in  bone  tissue, 
it  has  been  used  experimentally  in  the  treatment  of  bone  cancers  (115). 

MAGNESIUM 

During  a  drought  in  the  summer  of  1618  Henry  Wicker  (or  Wickes) 
discovered  on  the  common  at  Epsom,  Surrey,  a  small  hole  filled  with 
water.  To  his  astonishment,  not  one  of  his  thirsty  cattle  would  drink 
there.  This  bitter  water  was  found  to  have  a  healing  effect  on  external 
sores  and  to  be  useful  also  as  an  internal  medicament.  By  the  middle 
of  the  seventeenth  century,  Epsom  had  become  a  fashionable  spa, 
attracting  famous  visitors  from  the  continent  (40,  62). 

In  1695  Dr.  Nehemiah  Grew  published  a  dissertation  on  the  medicinal 
value  of  salt  from  these  wells  (41).  Dr.  Grew  prepared  solid  Epsom  salt 
from  this  well  water  and  recognized  it  as  a  unique  substance:  "The  Purg- 
ing bitter  Salt  .  .  .  does  differ  in  its  Nature  and  Species  from  all  other 
Salts"  (62,  69).  Nehemiah  Grew  in  England  and  Marcello  Malpighi  in 
Italy  laid  the  foundations  for  the  science  of  plant  anatomy  ( 70 ) . 

In  1726  John  Toland  said  of  the  Epsom  spring:  "these  aluminous 
waters  are  experienc'd  to  be  very  beneficial  . .  .;  the  salt  that  is  chymically 
made  of  'em  being  famous  over  all  Europe"  (40). 


522  DISCOVERY  OF  THE  ELEIvCENTS 

Since  the  supply  of  the  natural  salt  was  insufficient  to  meet  the 
demand  for  it,  it  was  soon  superseded  by  an  artificial  product.  Gilles- 
Egide-Fran^ois  Boulduc  stated  in  1731  that  if  all  this  salt  on  the  market 
came  from  the  Epsom  well,  the  latter  must  consist  entirely  of  salt  without 
any  water  (116). 

Dr.  Mendez,  a  physician  in  England,  found  after  long  searching 
that  the  artificial  Epsom  salt  came  from  two  salt  springs,  one  at  Limington, 
Hampshire,  and  the  other  at  Portsea  Island  near  Portsmouth.  Since  the 
liquor  from  the  salt  piles  there  was  very  bitter,  it  was  necessary  to  remove 
the  bitter  salt  from  the  sodium  chloride.  After  these  salts  had  crystallized 
out  together  in  canals  dug  in  the  earth,  the  mass  was  boiled  in  large 
vessels  until  completely  dissolved.  The  earthy  impurities  and  the  heavy 
concentrated  solution  of  sodium  chloride  sank  to  the  bottom.  As  long 
as  the  upper  layer  continued  to  be  bitter,  it  was  skimmed  off,  concen- 
trated, and  allowed  to  crystallize  to  form  the  artificial  Epsom  salt  (117). 
Boulduc  found  that  this  artificial  product  could  be  prepared  not  only 
from  the  mother  liquor  of  sea  salt  but  also  from  rock  salt  (116). 

According  to  Torbern  Bergman,  crystals  of  artificial  Epsom  salt 
from  sea  water  "are  sometimes  so  large  that  they  are  sold  for  Glauber's 
salt;  and  on  the  other  hand,  in  France,  Glauber's  salt,  being  reduced  to 
small  speculae,  by  agitating  it  during  the  crystallization,  is  sold  for 
Epsom  salt.  "These  frauds,"  said  he,  "are  indeed  of  little  consequence, 
yet  they  throw  a  veil  over  the  truth,  and  are  not  easily  discovered"  (42). 

Caspar  Neumann  (1683-1737)  stated  that  the  artificial  Epsom  salt 
was  prepared  at  Portsmouth  by  adding  sulfuric  acid  to  the  mother  liquors 
left  in  the  purification  of  sea  salt  imported  from  Spain  and  Portugal  (43). 
He  distinguished  clearly  between  Epsom  salt  and  the  "sal  mirabile  of 
Glauber"  (sodium  sulfate),  and  stated  that  "The  earth  of  the  bitter  purg- 
ing salt  is  called  Magnesia  alba.  ...  I  have  nowhere  met  with  this 
earth  in  the  mineral  kingdom.  .  .  ."  He  did  not  distinguish  between 
magnesia  alba  and  lime,  however  ( 43 ) . 

An  excellent  account  of  the  early  history  of  magnesia  is  to  be  found 
in  Torbern  Bergman's  "Physical  and  Chemical  Essays"  (42).  At  the 
beginning  of  the  eighteenth  century,  a  certain  canon  regular  sold  at  Rome 
a  secret  panacea  called  magnesia  alba,  or  Count  Palma's  powder.  In 
1707  Michael  Bernhard  Valentini  of  Giessen  revealed  the  method  of 
preparing  it  by  calcination  from  "the  last  lixivium  of  nitre/'  Two  years 
later,  Johann  Adrian  Slevogt  of  Jena  gave  an  easier  way  of  preparing  it 
by  precipitation.  Since  this  powder  effervesced  with  acids,  chemists  long 
confused  it  with  "calcareous  earth,"  or  calcium  carbonate,  which  they 
used  to  prepare  from  crabs'  eyes,  oyster  shells,  and  egg  shells.  Friedrich 
Hoffmann  (1660-1742)  observed,  however,  that  when  calcareous  earth 
was  treated  with  vitriolic  (sulfuric)  acid,  it  yielded  an  insipid  salt, 


ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM 


523 


whereas  magnesia  was  converted  by  similar  treatment  into  an  intensely 
bitter  one  (42). 

At  this  time  is  was  believed  that  when  carbonates  were  calcined 
they  combined  with  an  acrid  principle  from  the  fire  to  form  caustic 
alkalies.  In  1755,  however,  Dr.  Joseph  Black  (26)  of  Edinburgh  pub- 
lished a  famous  treatise  entitled,  "Experiments  upon  Magnesia  Alba, 
Quicklime,  and  some  other  Alkaline  Substances/*  in  which  he  proved 
that  carbonates  lose  weight  during  calcination  and  that  the  substance 


Johann  Rudolph  Glauber,  1604-1670. 

German  chemist  who  detected  sodium 
sulfate  (Glauber's  salt,  the  enixum  of 
Paracelsus)  in  water  from  a  spring 
near  Vienna  and  introduced  its  use 
into  medicine.  His  "Description  of 
New  Philosophical  Furnaces"  contains 
methods  for  the  preparation  of  pyro- 
ligneous  acid  and  the  mineral  acids. 
See  ref.  (63). 


expelled  is  carbon  dioxide,  "fixed  air."  In  this  treatise  he  showed  that 
magnesia  is  entirely  different  from  lime,  and  four  years  later  A.  S.  Marg- 
graf  in  Berlin  made  the  same  discovery  independently  (6,  IS,  20,  21,  38), 
Other  Magnesian  Minerals.  In  1760  A.  S.  Marggraf  analyzed  some 
Saxon  serpentine,  which,  because  of  its  property  of  becoming  hard  when 
burned,  was  then  supposed  to  be  a  clay,  or  mineral  containing  calcium 
or  aluminum.  "This  so-called  serpentine-stone,"  said  he,  "which  I  have 
used  in  the  following  experiments,  is  that  which  is  found  so  abundantly 
in. the  Saxon  mountains,  in  the  great  quarry  near  Zoplitz,  that  a  brisk 


524  DISCOVERY  OF  THE  ELEMENTS 

trade  is  carried  on,  near  and  far,  in  vessels  made  from  it.  It  is  of  various 
colors,  black,  gray,  greenish,  whitish,  pale  yellow,  with  red  veins  (or) 
spots,  intermingled  with  amianthus  (silky  asbestos);  of  varying  hardness, 
to  be  sure,  but  always  so  soft  that  all  kinds  of  vessels  can  be  turned  from 
it,  such  as  mortars,  boxes,  tea-  and  coffee-pots,  cups,  bowls,  dishes, 
warming-stones,  etc.  Although  it  is  for  this  reason  well  known  to  every- 
one, the  true  composition  and  base  of  this  stone  are  nevertheless  un- 
known" (118). 

Since  the  serpentine  did  not  cling  to  the  tongue  nor  gradually  dis- 
integrate in  water,  as  clays  do  even  after  moderate  heating,  Marggraf 
believed  that  it  must  contain  a  soluble  earth  entirely  distinct  from  alumina. 
When  he  decomposed  the  mineral  with  sulfuric  acid,  he  noticed  that 
a  residue  of  silicic  acid  remained  and  that  the  solution  contained  a 
peculiar  alkaline  earth  which  was  neither  lime  nor  alumina.  When  he 
evaporated  the  solution,  it  formed  no  alum  but  displayed  crystals  identical 
with  those  from  natural  Epsom  salt  and  easily  distinguishable  from  those 
of  selenite  (calcium  sulfate  dihydrate).  He  noticed  that  magnesium 
nitrate  is  deliquescent;  that  the  chloride  is  identical  with  that  obtained 
from  the  mother  liquor  of  common  salt  and  that  heat  decomposes  it 
with  loss  of  hydrogen  chloride;  that  the  acetate,  unlike  calcium  acetate, 
does  not  crystallize;  and  that  ignited  magnesia  does  not  become  hot  when 
treated  with  water  (118, 119, 120). 

Joseph  Black,  in  his  "Lectures  on  the  Elements  of  Chemistry,"  de- 
scribed some  of  the  minerals  which  even  in  the  eighteenth  century  were 
known  to  contain  magnesia.  "There  is  a  set  of  earthy  or  stony  substances," 
said  he,  "concerning  the  classing  of  which  fossilists  were  a  long  time 
undecided  and  disagreed.  Most  ranked  them  among  the  clays,  and 
Cronstedt  among  the  rest.  They  have  been  known  by  the  names 
steatites  [soapstone],  lapis  serpentinus  [serpentine],  lapis  nephriticus 
fa  kind  of  jade],  and  lapis  ollaris  [potstone].  ...  In  general  they  are 
soft  like  soap  or  suet;  so  soft  as  to  be  cut  or  turned.  ...  It  hardens  in 
the  fire  without  melting.  Hence  some  species  are  turned  into  vessels. 
This  is  the  lapis  ollaris.  Inverary  House  is  built  of  an  impure  species  of 
it.  Mr.  Margraaf  [sicl]  first  shewed  that  all  these  contain  more  or  less 
of  magnesia,  closely  combined  with  some  other  earthy  substances,  and 
often  with  much  iron,  by  which  they  are  tinged  with  the  green  colour, 
more  or  less  deep,  that  appears  in  many  of  them"  (118,  121). 

At  the  beginning  of  the  eighteenth  century,  J.-P.  de  Tournefort 
recognized  the  most  important  properties  of  amianthus,  or  silky  asbestos. 
""Tis  a  vulgar  Error,"  said  he,  "to  think  the  feather'd  Alum  to  be  the  same 
with  the  Lapis  Amianthus,  or  incombustible  Stone.  Whenever  I  ask'd 
for  feather  d  Alum,  either  in  France,  Italy,  England,  or  Holland,  they 
always  shewed  me  a  base  sort  of  Amianthus  brought  from  Carysto  in  the 


ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM  525 

Negropont:  it  is  easy  to  break  and  divide,  and  of  all  the  kinds  of 
Amianthus  is  certainly  the  most  despicable;  but  it  does  not  melt  or  con- 
sume either  in  Fire  or  Water,  any  more  than  the  Amianthus  of  Smyrna, 
Genoa,  and  the  Pyrenees.  To  make  short,  the  Amianthus  is  a  stony 
insipid  Substance  which  softens  in  Oil  and  thereby  acquires  Suppleness 
enough  to  be  spun  into  Threads:  it  makes  Purses  and  Handkerchiefs, 
which  not  only  resist  the  Fire,  but  are  whiten'd  and  cleansed  in  it.  The 
plumous  Alum,  contrariwise,  is  a  true  Salt,  not  differing  from  the  common 
Alum  otherwise  than  as  it  is  divided  into  small  Strings.  .  "  (122).  Marg- 


Side  View  of  the  ficole  Superieure  de  Pharmacie,  showing  the  laboratories 
for  practical  pharmacy. 


graf  later  determined  the  magnesia  in  amianthus,  a  fine,  silky  asbestos 
named  for  Amiandus  on  the  Island  of  Cyprus.  The  mines  there  have 
been  worked  since  ancient  times  (123). 

The  Indians  and  colonists  of  New  England  found  many  uses  for 
serpentine,  soapstone,  and  asbestos.  Per  Kalm,  in  describing  his  journey 
to  North  America  in  1748-51,  wrote  as  follows:  "Mr.  [Benjamin]  Franklin 
gave  me  a  piece  of  stone  which,  on  account  of  its  indestructibility  in  the 
fire,  is  made  use  of  in  New  England  for  making  melting  furnaces  and 
forges.  It  consists  of  a  mixture  of  lapis  ollaris,  or  serpentine  stone,  and 
of  asbest.  .  .  .  Another  stone  is  called  soapstone  by  many  of  the  Swedes, 
being  as  smooth  as  soap  on  the  outside.  They  make  use  of  it  for  rubbing 


526  DISCOVERY  OF  THE  ELEMENTS 

spots  out  of  their  cloaths If  the  people  can  get  a  sufficient  quantity 

of  this  stone,  they  lay  the  steps  before  the  houses  with  it,  instead  of 
bricks  .  .  .  ;  and  in  several  public  buildings,  such  as  the  house  of  assembly 
for  the  province,  the  whole  lower  wall  is  built  of  it.  ... 

"The  mountain  flax,"  said  Kalm,  "or  the  amiant  with  soft  fibres,  which 
can  easily  be  separated,  is  found  abundantly  in  Pensylvania  [sic],  .  .  . 
Mr.  Franklin  told  me  that,  twenty  and  some  odd  years  ago,  when  he 
made  a  voyage  to  England,  he  had  a  little  purse  with  him,  made  of  the 
mountain  flax  of  this  country,  which  he  presented  to  Sir  Hans  Sloane. 
I  have  likewise  seen  paper  made  of  this  stone.  .  .  . 

"The  old  boilers  or  kettles  of  the  Indians/3  continued  Kalm,  "were 
either  made  of  clay  or  of  different  kinds  of  potstone  [lapis  ollaris].  ...  A 
few  of  the  oldest  Swedes  could  yet  remember  seeing  the  Indians  boil 
their  meat  in  these  pots.  .  .  .  The  Indians,  notwithstanding  their  being 
unacquainted  with  iron,  steel,  and  other  metals,  have  learnt  to  hollow 
out  very  ingeniously  these  pots  or  kettles  of  potstone.  The  old  tobacco- 
pipes  of  the  Indians  are  likewise  made  of  clay  or  potstone  or  serpentine- 
stone"  (124). 

Thomas  Henry  mentioned  in  1789  another  magnesium  mineral,  "the 
Spuma  Maris,  an  earthy  substance,  from  which  the  Turkey  tobacco-pipes 
are  made"  (125).  This  was  the  hydrated  magnesium  silicate  known  as 
meerschaum.  For  the*  use  of  artists  and  potters,  Henry  published  a  list 
of  the  principal  compounds,  minerals,  and  rocks  containing  magnesium, 
and  gave  the  chemical  composition  of  each.  "Magnesia  as  prepared  for 
the  shops,"  said  he,  "would  be  too  expensive  for  the  purposes  of  manu- 
factures, which  may  perhaps  oftfen  be  equally  answered  by  using  it  in 
these  combined  forms"  (125). 

When  Sir  Humphry  Davy  isolated  a  little  magnesium  metal  in  the 
famous  experiments  already  described,  he  called  it  magnium  because, 
as  he  said,  the  word  magnesium  is  easily  confused  with  manganese. 
Nevertheless,  the  name  magnesium  has  persisted,  and  the  metal  is  no 
longer  known  by  the  one  which  Davy  gave  it. 

In  1792  Anton  Rupprecht  prepared  impure  magnesium  (contami- 
nated with  iron)  by  reduction  of  magnesium  oxide  with  carbon  and 
called  the  metal  "austrium"  in  honor  of  Austria  (68). 

The  quantity  of  metal  which  Davy  prepared  was  very  small,  and 
it  was  not  until  1831  that  it  was  first  prepared  in  a  coherent  form.  This 
was  done  by  the  French  chemist,  Antoine-Alexandre-Brutus  Bussy,  who 
was  born  at  Marseilles  on  May  29,  1794.  He  studied  at  the  Ecole  Poly- 
technique  for  a  time,  but  his  interest  in  chemistry  soon  led  him  to  aban- 
don his  military  career  and  to  become  apprenticed  to  a  pharmacist  After 
studying  pharmacy  at  Lyons  and  at  Paris  he  became  a  pupil  of  P.-J. 
Robiquet,  who  was  then  a  preparateur  in  chemistry  at  the  Ecole  de 


ALKALINE  EABTH  METALS,  MAGNESIUM,  CADMIUM 


527 


Pharmacie.     Bussy  graduated  in  pharmacy  in  1823   and   received  his 
medical  degree  in  1832. 

Although  most  of  his  researches  were  of  a  pharmaceutical  nature, 
he  published  in  1831  a  paper  entitled  "Sur  le  Radical  metallique  de  la 
Magnesie,"  in  which  he  described  a  new  method  of  isolating  magnesium, 
which  consisted  in  heating  a  mixture  of  magnesium  chloride  and  potas- 
sium in  a  glass  tube.  When  he  washed  out  the  potassium  chloride,  small, 
shining  globules  of  metallic  magnesium  remained  (8,  20,  27). 


Antoine-Alexandre-Brutus  Bussy,  1794- 
1882.  French  chemist,  pharmacist,  and 
physician.  Professor  of  chemistry  at  the 
Ecole  de  Pharmacie  in  Paris.  He  was 
connected  with  this  school  for  more  than 
fifty  years,  and  for  nearly  thirty  years  he 
served  as  its  director.  In  1831  he  ob- 
tained magnesium  in  coherent  form. 


For  several  years  Bussy  taught  pharmacology  in  the  medical  school 
at  the  Ecole  de  Pharmacie,  and  in  1856  he  served  as  president  of  the 
Academy  of  Medicine.  For  fifty-six  years  he  served  on  the  editorial 
staff  of  the  Journal  de  Pharmacie  et  de  Chimie.  He  died  at  Paris  on 
February  1,  1882,  at  the  age  of  eighty-seven  years  (22). 

Magnesium  in  Plants  and  Animals.  Even  in  the  eighteenth  century, 
chemists  realized  that  plants  contain  magnesia.  William  Lewis,  in  his 
notes  to  "The  Chemical  Works  of  Caspar  Neumann,  M.D.,"  said  in  1759 
that  "the  ashes  of  vegetables  freed  from  their  saline  parts  dissolve  readily 
and  plentifully  in  all  acids,  and  appear  to  be  similar  to  the  mineral  earth 
called  Magnesia,  or  the  earthy  basis  of  the  bitter  purging  Salts  of  mineral 
waters.  ...  It  forms  the  same  compounds  with  acids;  and  like  that 
earth  also,  it  acquires  no  acrimony  nor  any  change  of  its  quality  from 
fire.  ."(43). 


528  DISCOVERY  OF  THE  ELEMENTS 

"The  late  Dr.  Lewis"  said  Thomas  Henry,  "has  considered  the 
earth  which  is  obtained  from  vegetables,  after  incineration  and  washing, 
as  of  the  same  nature  with  Magnesia;  and  if  we  endeavour  to  trace  the 
origin  of  magnesian  earth,  it  may  appear  not  improbable  that,  as  all 
calcareous  earth  is  the  result  of  the  destruction  of  testaceous  animals,  so 
the  magnesium  arises  from  vegetables,  which  have  perished  and  under- 
gone some  process  in  the  great  laboratory  of  nature  whereby  they  are 
reduced  to  this  state.  By  putrefaction  they  are  altered  to  a  fine  black 
Mold.  And  it  may  be  that  Nature,  who  often  operates  by  slow  and  secret 
steps,  may  make  such  further  changes  as  to  convert  this  Mold  into 
magnesian  earth"  (125). 

L.  von  Crell  mentioned  in  1791,  in  a  footnote  to  J.  G.  Wallerius's 
paper  on  the  earths  derived  from  plants,  that  the  presence  of  magnesia 
in  plants  had  been  established  through  the  researches  of  Riickert  (126}. 
This  was  probably  G.  C.  A.  Riickert,  court  apothecary  at  Ingelfingen, 
who  published  a  book  on  agricultural  chemistry  in  1789. 

Richard  Willstatter  prepared  in  1906  some  very  pure  chlorophyll 
which  yielded  on  incineration  1.84  per  cent  of  ash,  1.67  per  cent  of  which 
was  magnesia.  The  ash  was  free  from  calcium  and  iron.  When  he  pre- 
pared chlorophyllin  from  phanerogams,  mono-  and  dicotyledons,  and 
gymnosperms,  from  Fucus,  from  the  stinging  nettle,  from  grass,  and  from 
pine  needles,  he  found  that  the  ash  always  contained  magnesium  and 
no  other  metal.  He  concluded  that  plants,  like  animals,  live  by  the 
catalytic  action  of  metals  which  they  contain  in  the  form  of  complex 
organic  compounds.  He  stated  that  assimilation  of  carbonic  acid  is  a 
reaction  of  the  basic  metal  magnesium,  which,  even  in  complex  organic 
molecules,  exhibits  great  reactivity.  He  compared  this  absorption  of 
carbon  dioxide  to  the  Grignard  synthesis.  Whereas  animals  live  by 
the  decomposition  of  organic  compounds  by  the  oxygen  in  their  blood, 
plants,  according  to  Willstatter,  live  synthetically  by  means  of  their 
magnesium  (127).  In  most  animals  the  oxygen  carrier  is  iron. 

Since  magnesium  is  a  constituent  of  the  chlorophyll  molecule,  it 
is  essential  to  the  growth  of  all  green  plants  (78).  It  occurs  in  all  the 
cells  and  fluids  of  the  human  body,  especially  in  bones  and  muscles  (82). 
E.  V.  McCollum  and  his  collaborators  have  proved  that  it  is  essential 
to  animal  Me.  The  principal  sources  of  magnesium  in  human  diets  are 
milk,  vegetables,  and  green  plants  (128,  129). 

Magnesium  from  Sea  Water.  Even  in  the  eighteenth  century,  Tor- 
bern  Bergman  knew  that  sea  water  derives  its  bitter  taste  from  magnesium 
chloride  (ISO,  125).  On  January  21,  1941,  the  Dow  Chemical  Company 
produced  at  Freeport,  Texas,  an  ingot  of  magnesium  which  was  the  first 
commercial  ingot  of  any  metal  ever  to  be  taken  from  sea  water  (131). 


ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM  529 

CADMIUM 

Cadmium  was  discovered  in  1817  by  Dr.  Friedrich  Stromeyer,  a 
professor  of  chemistry  and  pharmacy  at  Gottingen  University.  He  was 
born  on  August  2,  1776,  at  a  time  when  the  phlogiston  theory  was  draw- 
ing its  last  breath  (8).  After  studying  chemistry,  botany,  and  pharmacy 
in  his  native  city  of  Gottingen,  he  worked  in  Paris  under  the  great  master 
of  analytical  chemistry  N.-L.  Vauquelin.  Following  the  example  of  this 


Science   Service 

Friedrich  Stromeyer,  1776-1835.  German  physician,  botanist, 
chemist,  and  pharmacist.  Inspector-general  of  all  the  Hano- 
verian apothecary  shops.  Discoverer  of  the  element  cadmium. 
His  collection  of  thirty  mineral  analyses  is  a  classic  of  analyti- 
cal chemistry. 


530  DISCOVERY  OF  THE  ELEMENTS 

famous  teacher,  he  devoted  himself  almost  entirely  to  the  analysis  of 
minerals  (9). 

In  1802  he  became  a  Frwatdozent  in  the  faculty  of  medicine  at 
Gottingen,  and  was  rapidly  promoted  until  in  1810  he  became  a  full 
professor  (Professor  ordinarius).  In  the  German  universities,  as  in  cer- 
tain American  ones,  professors  frequently  hold  government  offices.  Dr. 
Stromeyer  was  the  inspector-general  of  all  the  apothecaries  of  Hanover. 
On  an  inspection  trip  to  Hildesheim  in  the  autumn  of  1817  he  noticed  that 
a  certain  preparation  which,  according  to  the  Hanoverian  Pharmacopoeia, 
ought  to  have  contained  zinc  oxide,  contained  zinc  carbonate  instead. 
The  events  which  followed  were  described  by  Dr.  Stromeyer  in  his  letter 
to  Dr.  J.  S.  C.  Schweigger  written  on  April  26,  1818: 

As  I  was  last  harvest  inspecting  the  apothecaries'  shops  in  the  principality 
of  Hildesheim,  in  consequence  of  the  general  inspection  of  the  apothecaries  of 
the  kingdom  having  been  entrusted  to  me  by  our  most  gracious  Regency,  I 
observed  in  several  of  them,  instead  of  the  proper  oxide  of  zinc,  carbonate  of 
zinc,  which  had  been  almost  entirely  procured  from  the  chemical  manufactory 
at  Salzgitter.  This  carbonate  of  zinc  had  a  dazzling  white  colour;  but  when 
heated  to  redness,  it  assumed  a  yellow  colour,  inclining  to  orange,  though  no 
sensible  portion  of  iron  or  lead  could  be  detected  in  it. 

In  an  attempt  to  determine  why  this  substitution  had  been  made,  Dr. 
Stromeyer  visited  the  pharmaceutical  firm  at  Salzgitter: 

When  I  afterwards  visited  Salzgitter,  during  the  course  of  this  journey  [said 
he]  and  went  to  the  chemical  manufactory  from  which  the  carbonate  of  zinc 
had  been  procured;  and  when  I  expressed  my  surprise  that  carbonate  of  zinc 
should  be  sold  instead  of  oxide  of  zinc,  Mr.  Jost,  who  has  the  charge  of  the 
pharmaceutical  department  of  the  manufactory,  informed  me  that  the  reason 
was,  that  their  carbonate  of  zinc,  when  exposed  to  a  red  heat,  always  assumed 
a  yellow  colour,  and  was  on  that  account  supposed  to  contain  iron,  though 
the  greatest  care  had  been  taken  beforehand  to  free  the  zinc  from  iron,  and 
though  it  was  impossible  to  detect  any  iron  in  the  oxide  of  zinc  itself. 

The  fact  that  the  zinc  carbonate  could  not  be  converted  into  the 
oxide  without  discoloration  interested  Dr.  Stromeyer  greatly: 

This  information  [said  he]  induced  me  to  examine  the  oxide  of  zinc  more 
carefully,  and  I  found,  to  my  great  surprise,  that  the  colour  which  is  assumed 
was  owing  to  the  presence  of  a  peculiar  metallic  oxide,  the  existence  of  which 
had  not  hitherto  been  suspected.  I  succeeded  by  a  peculiar  process  in  freeing 
it  from  oxide  of  zinc,  and  in  reducing  it  to  the  metallic  state  .  .  .  (10}. 

^  His  method  of  obtaining  the  metal  was  as  follows.  He  dissolved  the 
impure  zinc  oxide  in  sulfuric  acid  and  passed  in  hydrogen  sulfide.  After 
filtering  and  washing  the  precipitate  of  mixed  sulfides,  he  dissolved 
it  in  concentrated  hydrochloric  acid  and  evaporated  to  dryness  to  drive 


ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM 


531 


off  excess  acid.  After  dissolving  the  residue  in  water,  he  added  a  sufficient 
excess  of  ammonium  carbonate  solution  to  redissolve  any  zinc  and  copper 
that  may  have  been  precipitated.  Since  the  carbonate  of  the  new  element 
was  not  soluble  in  excess  ammonium  carbonate,  Dr.  Stromeyer  filtered 
it  off,  washed  it,  and  ignited  it  to  the  oxide.  After  mixing  the  brown 
oxide  with  lampblack  in  a  glass  or  earthen  retort,  he  heated  the  mixture 
to  moderate  redness.  Upon  opening  the  retort  he  found  a  bluish  gray 
metal  with  a  bright  luster  (10). 


Exhibit  of  Drugs  and  Medicinals  at  the  Ecole  Superieure  de  Pharmacie. 

Vauquelin  was  the  director  of  this  school  from  the  time  of  its  reorganization 
in  1803  until  his  death  in  1829. 


However,  since  he  had  only  three  grams  of  the  new  metal,  he  was 
unable  at  first  to  make  a  thorough  study  of  its  properties.  Fortunately, 
he  soon  received  more  of  it  from  an  unexpected  source,  for  in  the  same 
letter  to  Dr.  Schweigger  he  wrote: 

I  am  happy,  therefore,  to  be  able  to  inform  you,  that  within  these  few  days, 
through  Mr.  Hermann,  of  Schonebeck,  and  Dr.  Roloff,  of  Magdeburg,  who 
took  an  interest  in  this  metal,  I  have  been  placed  in  a  situation  which  will 
enable  me  to  carry  my  experiments  further.  During  the  apothecary's  visitation 
in  the  state  of  Magdeburg  some  years  ago,  there  was  found  in  the  possession 
of  several  apothecaries,  a  preparation  of  zinc  from  Silesia,  made  in  Hermann's 
manufactory  at  Schonebeck,  which  was  confiscated  on  the  supposition  that  it 
contained  arsenic,  because,  when  dissolved  in  acids,  and  mixed  with  sul- 


532  DISCOVERY  OF  THE  ELEMENTS 

phuretted  hydrogen,  it  let  fall  a  yellow  precipitate,  which,  from  the  chemical 
experiments  made  on  it,  was  considered  as  orpiment. 

This  fact  [continued  Stromeyer]  could  not  be  indifferent  to  Mr.  Hermann, 
as  it  affected  the  credit  of  his  manufactory,  and  the  more  especially  as  the 
Medicinal  Counsellor  Roloff,  who  had  assisted  at  the  Apothecaries*  visitation, 
had  drawn  up  a  statement  of  the  whole,  and  sent  it  to  Hufeland,  who  published 
it  in  the  February  number  of  his  Medical  Journal.  He,  therefore,  subjected 
the  suspected  oxide  of  zinc  to  a  careful  examination;  but  he  could  not  succeed 
in  detecting  any  arsenic  in  it  (24), 

He  then  requested  the  Medical  Counsellor  Roloff  (23)  to  repeat  his 
experiments  on  the  oxide  once  more.  This  he  did  very  readily  and  he  now 
perceived  that  the  precipitate  which  had  at  first  been  taken  by  him  for 
orpiment,  was  not  so  in  reality;  but  owed  its  existence  to  the  presence  of 
another  metal,  having  considerable  resemblance  to  arsenic,  but  probably  new. 
To  obtain  full  certainty  on  the  subject,  both  the  gentlemen*  had  recourse  to 
me,  and  have  sent  me,  within  these  few  days,  both  a  portion  of  the  Silesian 
oxide  of  zinc  and  specimens  of  the  orpiment-like  precipitate  and  of  the  metal 
extracted  from  it,  with  the  request  that  I  would  subject  these  bodies  to  a  new 
examination,  and  in  particular  that  I  should  endeavour  to  ascertain  whether 
they  contained  any  arsenic  (10). 

Dr.  Stromeyer  soon  surmised  that  the  metal  which  Mr.  K.  S.  L. 
Hermann  and  Dr.  J.  C.  H.  Roloff  had  extracted  from  the  Silesian  zinc 
oxide  was  the  same  as  the  one  he  had  obtained  from  the  Salzgitter  prod- 
uct (31,  35,  39). 

From  the  particulars  already  stated  [said  he]  I  considered  it  as  probable 
that  this  Silesian  oxide  of  zinc  contained  likewise  the  metal  which  I  had  dis- 
covered; and  as  it  gives  with  sulphuretted  hydrogen  a  precipitate  similar  in 
colour  to  orpiment,  I  considered  this  to  be  the  reason  why  the  oxide  was  sup- 
posed to  contain  arsenic.  Some  experiments  made  upon  it  fully  confirmed  this 
opinion.  I  have,  therefore,  informed  Mr.  Hermann  of  the  circumstance  by  the 
post;  and  I  shall  not  fail  to  give  the  same  information  to  Medicinal  Counsellor 
Roloff,  whose  letter  I  received  only  the  day  before  yesterday 

This  discovery  gave  great  satisfaction  and  relief  to  Mr.  Hermann 
because  it  again  brought  his  pharmaceutical  establishment  into  good 
standing,  and  it  also  gave  Dr.  Stromeyer  the  opportunity  to  make  a  more 
thorough  study  of  the  new  metal  and  its  compounds.  Because  this  metal 
is  so  frequently  found  associated  with  zinc,  he  named  it  cadmium, 
meaning  cadmium  fornacum  or  furnace  calamine.  In  the  researches 
which  led  to  this  discovery,  he  was  assisted  by  two  of  his  students,  Mr. 
Manner  of  Brunswick  and  Mr.  Siemens  of  Hamburg. 

W.  Meissner  (36)  of  Halle  and  C.  Karsten  (25)  of  Berlin,  without 

*  Dr.  Roloff  (31 )  explained  that  this  was  not  done  to  settle  a  dispute. 


ALKALINE  EABTH  METALS,  MAGNESIUM,  CADMIUM  533 

any  knowledge  of  the  work  done  by  Stromeyer,  Roloff,  and  Hermann, 
also  discovered  cadmium  independently  (11).  Meissner  analyzed  two 
products  from  the  Schonebeck  plant  sent  him  by  Superintendent  of  Mines 
von  Veltheim,  one  of  which  proved  to  be  the  carbonate  and  the  other 
the  sulfide  of  the  new  metal.  By  dissolving  the  carbonate  in  nitric  acid 
and  placing  a  rod  of  pure  zinc  in  the  solution,  he  obtained  a  voluminous, 
light  gray  deposit.  When  he  washed  and  dried  it  and  ground  the  resulting 
powder  in  an  agate  mortar,  it  exhibited  a  metallic  luster.  Meissner  made 
a  careful  study  of  the  metal  and  its  compounds. 

In  1817,  perhaps  as  a  result  of  his  great  discovery,  Dr.  Stromeyer 
received  the  honorary  title  of  Hofrath,  or  court  counselor.     After  pub- 


Old  Filter  Stand 


lishing  many  papers  on  mineralogy  and  chemistry,  and  serving  his  uni- 
versity for  many  years  as  an  inspiring  teacher,  he  died  on  August  18, 
1835,  in  the  city  where  he  was  born  and  where  he  had  spent  most  of 
his  life  (8,  65). 

In  1821  Nils  Nordenskiold  wrote  to  Berzelius,  "Stromeijer  [sic]  has 
the  finest  and  neatest  laboratory  I  have  yet  seen  in  Germany,  and  is 
certainly  one  of  the  few  whose  analyses  are  somewhat  reliable.  Never- 
theless his  procedures  differ  from  yours  in  many  important  respects.  I 
shall  take  the  liberty  of  mentioning  a  few  of  the  differences  I  have 
noticed.  One  sees  no  filter  stand.  All  filtrations  are  made  in  glass 
cylinders  such  as  come  with  our  brandy  gauges,  one  foot  high  and  from 
3  to  1  inch  in  diameter;  as  the  funnels  are  wider,  they  are  simply  placed 
over  the  edge  of  the  glass;  the  liquid  spatters  around,  but  the  filter  takes 


534  DISCOVERY  OF  THE  ELEMENTS 

up  that  which  spatters  out.  The  filter  is  folded  like  the  French  ones  and 
always  extends  over  the  rim  of  the  funnel  The  filter  is  not  burned.  The 
solutions  are  also  precipitated  in  the  above-mentioned  glass  cylinders,  and 
the  digestions  are  made  in  retorts  or  small  flasks  with  long  necks  and  thin 
bottoms.  The  sandbath  is  not  used;  the  heating  is  done  over  the  free  flame 
or  on  hot  plates.  In  regard  to  reagents,  I  have  noticed  that  he  prefers  to 
use  the  fixed  alkalies  as  precipitating  agents  instead  of  ammonium  hy- 
droxide which  I  believe  involves  difficulty  in  washing  the  filter,  especially 
such  as  they  use  here.  The  balance  Stromeyer  uses  is  very  good,  but  one 
has  to  walk  through  a  hall  to  reach  the  room  where  it  is  kept"  (61). 

Cadmium  from  Zinc  Ores.  In  an  editorial  note  in  volume  59  of  his 
Annalen  der  Physik,  L.  W.  Gilbert  gave  the  following  quotation  from  a 
"Report  of  a  metallurgical  trip  through  Silesia  in  Professor  Kastner's 
German  Gewerbsfreunde,  1818,  Number  24:  In  Silesia  and  in  the  nearby 
parts  of  Poland,  zinc  is  obtained  only  from  calamine,  ...  In  the  zinc 
smelters  one  sees  the  metal  burning  with  a  bright  flame  from  all  the 
condensers,  and  in  the  receptacles  where  the  separated  metal  collects, 
piles  of  zinc  oxide  are  always  found."  Gilbert  then  added  that  the  zinc 
oxide  in  which  Hermann  discovered  cadmium  probably  came  from  these 
piles  (132). 

Dr.  Stromeyer  detected  cadmium  in  tutty  and  other  kinds  of  zinc 
oxide,  in  metallic  zinc,  in  Silesian  zinc  ores,  and  in  several  blendes,  es- 
pecially one  from  Przibram,  Bohemia,  which  contained  2  or  3  per  cent 
of  it  (10,  24).  Thus  it  is  evident  that  cadmium  was  first  discovered  in 
substances  of  which  it  is  merely  a  non-essential  constituent. 

In  a  letter  to  the  Annals  of  Philosophy,  dated  Cambridge,  February 
18,  1820,  Edward  Daniel  Clarke  wrote  as  follows:  "Some  varieties  of 
radiated  blende  from  Przibram  in  Bohemia  are  described  by  Stromeyer 
as  containing  two  or  three  per  cent  of  cadmium.  At  a  sale  ...  in 
London,  I  procured  specimens  of  the  particular  mineral  thus  alluded  to, 
which  were  sold  under  the  name  of  splendent  -fibrous  blende  from 
Przibram,  pronounced  Pritzbram.  I  found  afterwards  that  they  had  been 
brought  to  England  by  Mr.  J.  Sowerby  of  Lisle-street,  a  dealer  in 
minerals.  .  .  »  Upon  my  return  to  Cambridge,  I  endeavoured  to  obtain 
cadmium  from  this  ore,  and  succeeded  .  .  ."  (133).  Clarke  also  found 
this  element  in  the  zinc  silicate  from  Derbyshire,  England,  and  his  results 
were  soon  confirmed  by  W.  H.  Wollaston  and  J.  G.  Children.  In  1822 
Clarke  published  a  paper  on  the  presence  of  cadmium  in  commercial 
sheet  zinc  (134). 

In  the  same  year,  William  Herapath  analyzed  some  sublimate  from 
a  zinc  smelter,  and  found  from  12  to  20  per  cent  of  cadmium  in  it.  Since 
cadmium  is  even  more  volatile  than  zinc,  much  of  it  was  lost.  Herapath 


ALKALINE    EARTH    METALS    MAGNESIUM,    CADMIUM  535 

suggested  a  modification  o£  the  zinc  distillation  process  which  would 
make  it  possible  to  recover  the  cadmium  (135). 

Greenockite  the  First  Cadmium  Mineral.  In  1841  Charles  Murray 
Cathcart  (Lord  Greenock)  discovered  a  rare  mineral  of  which  cadmium 
is  an  essential  constituent.  Greenockite,  or  cadmium  sulfide,  "was  found 
in  the  course  of  excavating  the  Bishopton  Tunnel,  near  Port  Glasgow." 
Lord  Greenock  (second  Earl  Cathcart)  was  born  in  1783,  entered  the 
army  at  a  very  early  age,  and  devoted  most  of  his  life  to  military  affairs 
in  Spain,  Holland,  Scotland,  and  Canada.  He  served  as  Commander- 
in-chief  of  the  British  forces  in  North  America  and  in  1846-47  as  Gover- 
nor-general of  Canada  (136). 

The  Royal  Staff  Corps  which  he  commanded  was  a  scientific  one, 
which  maintained  a  museum  of  objects  collected  by  its  members.  After 
Lord  Greenock's  death  in  1859,  Lord  Neaves  said  before  the  Royal 
Society  of  Edinburgh,  "If  it  be  considered  how  total  a  revolution  of 
habits  and  employments  was  involved  in  the  transition  from  his  military 
to  his  civil  life,  it  is  remarkable  what  success  and  energy  attended  his 
scientific  career  during  the  years  he  spent  among  us.  He  was  distin- 
guished by  persevering  and  acute  observation  in  what  regarded  geological 
and  mineralogical  research,  which  he  carried  on  in  a  minute,  laborious, 
and  systematic  manner.  He  detected  many  interesting  phenomena  in  the 
very  neighbourhood  of  Edinburgh,  which  had  escaped  those  who  had 
lived  there  always.  His  conversation  on  these  subjects  was  pre-eminently 
instructive;  and  it  is  believed  that  he  never  took  an  ordinary  walk  without 
bringing  home  some  specimen,  or  at  least  some  remembered  fact,  which 
served  him  for  subsequent  meditation.  He  was  fond  of  the  society  of 
men  of  science,  and  his  continued  interest  in  the  Royal  Society  formed 
an  essential  element  in  its  prosperity"  (137). 

Fluorescent  Lighting.  An  important  application  of  the  cold  light 
from  certain  compounds  of  zinc,  cadmium,  and  other  elements  of  Group 
II  of  the  periodic  system  is  the  modern  fluorescent  lamp.  A  long  tube, 
containing  an  inert  gas  at  low  pressure  and  a  few  droplets  of  mercury,  is 
constructed  with  an  electrode  at  each  end.  This  tube  has  an  inside  coating 
of  some  stable,  fluorescent  substance  which  will  absorb  the  resonance  line 
of  a  low-pressure  mercury  discharge  in  the  ultraviolet  at  2537  Angstrom 
units  and  reradiate  this  energy  in  a  desirable  part  of  the  visible  spectrum 
(57).  The  basic  part  of  the  fluorescent  compound  used  always  contains 
a  lower  atomic  weight  metal  from  Group  II.  Zinc  silicate,  for  example, 
gives  a  green  fluorescence;  cadmium  silicate  and  the  borates  of  cadmium 
and  zinc  give  pink;  magnesium  tungstate  and  zinc  beryllium  silicate  give 
white  light,  and  calcium  tungstate  gives  blue.  Although  the  sulfides  of 
zinc  and  cadmium  are  sometimes  used  in  fluorescent  paints,  they  are 
not  stable  enough  for  use  inside  fluorescent  lamps  (57). 


538  DISCOVERY  OF  THE  ELEMENTS 

LITERATURE  CITED 

(1)  DAVY,  DR.  J.,  "The  Collected  Works  of  Sir  Humphry  Davy,  Bart,"  Vol.  1, 

Smith,  Elder  and  Co.,  London,  1839,  p.  235.    Poem  by  Sir  H.  D. 

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140-4. 

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(5)  Ibid.,  vol.  2,  pp.  138-40. 

(6)  Ibid.,  Vol.  2,  pp.  153-5. 

(7)  DAVY,  DR.  J.,  "Memoirs  of  the  Life  of  Sir  Humphry  Davy,  Bart.,"  Vol.   1, 

Longman,  Rees,  etc.,  London,  1836,  pp.  395-6. 

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ALKALINE  EAUTH  METALS,  MAGNESIUM,  CADMIUM  537 

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ALKALINE  EARTH  METALS,   MAGNESIUM,  CADMIUM  539 

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540  DISCOVERY  OF  THE  ELEMENTS 

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ALKALINE  EARTH  METALS,  MAGNESIUM,  CADMIUM  541 

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Martin  Helnrich  KIaproth3  1743-1817.  German  analytical  chemist. 
First  professor  of  chemistry  at  the  University  of  Berlin.  In  1810  he 
published,  with  F.  Wolff,  a  chemical  dictionary  containing  refer- 
ences to  the  researches  cited  therein.  Klaproth's  six-volume  "Bei- 
trage  zur  chemischen  Kenntniss  der  Mineralkorper"  is  a  collection 
of  his  remarkable  mineral  analyses.  He  rediscovered  Gregorys 
"menachanite/*  made  a  thorough  study  of  its  properties,  and  re- 
christened  it  titanium. 


Es  hat  wohl  nie  eine  Wissenschaft,  in  einem  kleinern 
Zeitraume,  raschere  Fortschritte  gemacht,  als  die 
chemische  Naturkenntniss  (l)—No  science  has  ever 
made  more  rapid  progress  in  a  shorter  time  than 
chemistry. 


21 

Elements  isolated  with  the  aid  of 
potassium  and  sodium 


The  earths  of  the  titanium  group  had  a  cosmopolitan  origin. 
The  German  chemist  Klaproth  discovered  zirconia  in  1789  while 
analyzing  a  zircon  from  Ceylon.  Two  years  later  the  English 
clergyman  William  Gregor  found  titaniaf  or  "menachanite"  in  a 
black  sand  from  his  own  parish  in  Cornwall,  but  announced  his 
discovery  in  such  a  modest  manner  that  it  made  little  impression 
on  the  scientific  world.  Klaproth  rediscovered  this  earth  four 
years  later  in  a  Hungarian  red  schorl,  and  named  it  "Titanerde" 
or  titania.  Hisinger  and  Berzelius  discovered  ceria  in  1803  while 
investigating  the  Swedish  mineral  "heavy  stone  of  Bastnas"  now 
known  as  cerite.  Berzelius  found  thoria,  the  last  of  these  earths, 
in  1829  in  a  specimen  of  thorite  that  had  been  sent  to  him  from 
an  island  off  the  coast  of  Norway.  The  difficult  isolation  of  the 
metals  titanium,  cerium,  zirconium,  and  thorium  was  accomp- 
lished by  various  methods  involving  the  powerful  reducing 
action  of  sodium  and  potassium. 

ZIRCONIUM 


t  irconium  minerals  are  widely  distributed  in  Nature,  and  have 
been  used  for  centuries.  In  his  enraptured  description  of  the  four-square 
city,  Saint  John  the  Divine  mentioned  the  jacinth  (or  hyacinth)  as  one 
of  the  twelve  precious  stones  that  garnished  the  foundations  of  the  city 
wall  (14). 

Although  zircon  was  frequently  used  by  the  ancients  for  intagli,  and 
although  hyacinth  and  jargon  were  well  known  in  the  Middle  Ages,  the 
presence  in  these  minerals  of  an  unknown  metal  was  not  suspected  until 
near  the  end  of  the  eighteenth  century.  The  earth  zirconia  was  over- 
looked because  of  its  great  similarity  to  alumina,  and  it  took  the  analytical 
skill  of  a  Klaproth  to  detect  it. 

In  1787  Johann  Christian  Wiegleb  analyzed  a  zircon  from  Ceylon  and 
reported  only  silica,  with  small  amounts  of  magnesia,  lime,  and  iron  (54). 
Only  two  years  later,  Klaproth  discovered  the  earth  zirconia  in  a  jargon, 

543 


544 


DISCOVERY  OF  THE  ELEMENTS 


one  of  "the  rough  or  uncut  precious  stones  coming  from  Ceylon.  .  .  . 
Rome  de  lisle,"  said  he,  "was  the  first,  to  my  knowledge,  who  mentions 
these  gems  as  a  particular  species  of  stones;  giving  them  the  name  Jargon 
of  Ceylon  and  stating  their  weight,  according  to  Brisson's  experiments, 
at  4.416.  Other  mineralogists  and  writers  who  notice  this  stone  class  it- 
some  with  the  sapphire,  others  with  the  topaz,  others  with  the  ruby, 
others  with  the  diamond,  and  some  with  the  hyacinth.  But  Werner  has 
assigned  to  it  a  peculiar  place  in  the  mineralogic  system,  immediately 
under  the  diamond  and  the  chrysoheryl,  and  called  it  Zircon  (Silex 


Baron  Louis-Bernard  Guyton  de 
Morveau,  1737-1816.  French  attorney 
and  chemist.  Professor  of  chemistry  at 
the  Ecole  Polytechnique  from  1794  to 
1815.  With  Lavoisier,  Fourcroy,  and 
Berthollet  he  brought  chemical  nomen- 
clature into  accord  with  modern  views 
on  combustion.  He  made  the  first  seri- 
ous researches  on  the  structure  of  steel. 


circonius}"  (55).  Klaproth  named  the  earth  Zirkonerde,  or,  as  one  says 
in  English,  zirconia  (9,  31,  32).  All  analyses  of  zirconium  minerals  made 
before  the  discovery  of  this  earth  were  incorrect.  The  celebrated  Torbem 
Bergman,  for  example,  had  reported  the  following  composition  for  a 
certain  hyacinth  from  Ceylon: 

Silica  Alumina  Iron  Oxide  Lime 

25%  40%  13%  20% 

When  Klaproth  analyzed  the  same  specimen  he  found: 

Silica  Iron  Oxide  Zirconia    (Jargonia  ) 

25%  0.5%  70% 

His  results  were  soon  confirmed  by  Guyton  de  Morveau,*  who  extracted 
the  same  earth  from  a  hyacinth  from  Expailly,  France,  and  by  N.-L. 
Vauquelin  (9,  33,  34,  35).  In  1795  Klaproth  detected  zirconia  in  a 

*  During  the  Revolution,  the  scientific  papers  of  Morveau  were  signed  "Cit[oyen] 
Guyton." 


ELEMENTS  ISOLATED  WITH  THE  AID  OF  K  AND  NA  545 

hyacinth  from  Ceylon  (56).  Jargon  and  hyacinth  are  both  forms  of 
the  mineral  now  known  as  zircon,  zirconium  silicate,  ZrSiO4.  An  im- 
portant commercial  source  of  zirconium  is  the  native  zirconia,  or  badde- 
leyite,  of  Brazil  (37). 

In  1808  Sir  Humphry  Davy  tried  in  vain  to  decompose  zirconia  with 
the  electric  current,  but  Berzelius  (36)  finally  obtained  the  metal  in  1824 
by  heating  a  dry  mixture  of  potassium  and  potassium  zirconium  fluoride 
in  a  very  small  closed  iron  tube  placed  inside  a  platinum  crucible.  After 
the  quiet  reaction  had  taken  place,  he  cooled  the  tube  and  placed  it  in 
distilled  water,  whereupon,  to  use  his  own  words,  "There  fell  from  the 
tube  a  black  powder  as  fast  as  the  salt  dissolved,  and  at  the  same  time 
there  was  evolved  a  small  quantity  of  hydrogen.  .  .  .  The  zirconium  ob- 
tained in  this  manner  is  easily  deposited.  It  can  be  washed  with  water 
without  oxidizing.  Washed  and  dried,  it  forms  a  black  powder  resembling 
charcoal,  which  cannot  be  compressed  nor  polished  like  a  metal"  (15). 

Although  Berzelius'  method  yielded  impure  zirconium,  highly  con- 
taminated with  zirconia,  he  had  chosen  his  materials  with  great  scientific 
acumen  (37).  Through  the  attempts  of  many  research  workers,  in- 
cluding Ludwig  Weiss  and  Eugen  Naumann  (38),  Edgar  Wedekind  (39), 
and  Henri  Moissan  (40),  zirconium  of  higher  and  higher  purity  was 
obtained.  Finally,  in  1914,  D.  Lely,  Jr.,  and  L.  Hamburger  (41)  of  the 
research  staff  of  the  Philips  Metal-Incandescent  Lamp  Works  in  Eind- 
hoven, Holland,  obtained  the  metal  100  per  cent  pure.  Their  method 
consisted  in  heating  a  mixture  of  the  tetrachloride  and  sodium  in  a  bomb, 
using  the  electric  current  as  the  source  of  heat.  The  metal  consisted  of 
laminae  which  could  be  pressed  into  rods,  drawn  into  wire,  or  burnished 
to  a  bright,  mirror-like  surface. 

The  element  is  still  best  known,  however,  in  the  form  of  its  oxide. 
Zirconia  linings  for  metallurgical  furnaces  are  very  permanent,  and,  be- 
cause of  their  low  heat  conductivity,  may  be  made  very  thin.  Zirconia 
refractories,  such  as  crucibles,  are  very  resistant  to  the  action  of  heat, 
slags,  and  most  acids,  and  may  safely  be  plunged  into  water  while 
red-hot  (42). 

TITANIUM 

Joseph  Priestley  was  not  the  only  English  clergyman  to  discover  a 
new  element.  The  Reverend  William  Gregor  met  with  similar  good 
fortune.  He  was  born  in  1761  at  Trewarthenick  in  the  parish  of  Cornelly, 
Cornwall,  on  Christmas  Day,  1761.  He  graduated  in  1784  from  St.  John's 
College,  Cambridge,  where  he  excelled  in  mathematics  and  the  classics 
and  was  awarded  a  prize  for  excellence  in  Latin  prose.  After  receiving 
his  master's  degree  three  years  later,  he  took  charge  of  the  rectory  at 


546  DISCOVERY  OF  THE  ELEIMENTS 

Deptford,  near  Totnes,  which  his  father  had  purchased  for  him,  and  later 
served  for  a  time  at  Bratton  Clovelly,  Devonshire  (2).  Most  of  his  life, 
however,  was  spent  at  the  rectory  of  Creed,  in  Cornwall  He  displayed 
great  talent  for  landscape  painting,  etching,  and  music.  Through  at- 
tendance at  some  lectures  at  Bristol,  he  became  interested  in  chemistry 
and  analytical  mineralogy  (47}. 


IV. 


te,  eipett  in  Cornmaff 
ttm  magnttifdjenSattt);  t>o 
<Btliiam  ©tegor  *). 

f*  i*  ^\wfrt  6anb  fcriefc  in  prefer 
****'  in  wen* 
t»  ttt  ^wf 

^ieM  2W  fltcgt  tin  &acfc,  txffcn 
in  te 


;*Mgt  tfofrafctfti*  mit 
$$Eftet  finb  t>on 
fnnc  bejtimoitc  ^tgor. 


6f  me 


mit  rincm 


Introduction  to  the  Reverend 
William  Gregorys  Original 
Paper  on  Titanium.,  or  "Mena- 
chanite,"  Crell's  Annalen, 
1791. 


He  was  fascinated  by  the  minerals  of  England,  and  acquired  such 
great  skill  in  analyzing  them  that  Berzelius  and  other  competent  judges 
referred  to  him  as  "a  famous  mineralogist"  (3).  He  was  a  founder  and 
honorary  member  of  the  Royal  Geological  Society  of  Cornwall,  and  his 
analyses  of  such  substances  as  bismuth  carbonate,  topaz,  wavellite. 


ELEMENTS  ISOLATED  WITH  THE  AID  OF  K  AND  NA 


547 


uranium  mica  (Uranglimmer)  (16),  and  native  lead  arsenate  (17)  were 
of  high  excellence  (4). 

The  most  interesting  mineral  that  Mr.  Gregor  ever  analyzed,  however, 
was  a  black,  magnetic  sand  from  the  Menachan  valley  in  his  own  parish. 
His  account  of  this  analysis,  as  it  appeared  in  CrelTs  Annalen  in  1791, 
was  introduced  by  the  following  editorial  note: 

Mr.  Gregor  did  me  the  special  favor  of  sending  the  manuscript  of  this 
paper  for  insertion  in  the  Annalen,  the  translation  of  which  from  the  English 
by  my  eldest  son  Carl,  I  have  the  honor  to  present  to  German  analytical 
chemists. 


D.     Lorentz     von     Crell,     1744-1816. 

Editor  of  Chemische  Annalen  filr  die 
Freunde  der  Naturlehre,  Arzneigelahrt- 
heit,  Haushaltungskunst  und  Manufak- 
turen  and  of  Crell's  Neues  Chemisches 
Archiv.  Professor  of  chemistry  and 
counselor  of  mines  at  Helmstadt. 


The  Edgar  Fahs  Smith  Memorial  Collection, 
University  of  Pennsylvania 

The  paper  begins  with  a  minute  description  of  the  sand: 

This  sand  [said  Mr.  Gregor]  is  found  in  large  quantity  in  a  valley  of  the 
Menachan  parish  in  the  county  of  Cornwall.  Through  this  valley  there  flows  a 
stream  whose  principal  source  is  in  the  valleys  of  Gonhilly.  The  sand  is  black, 
and  in  external  appearance  resembles  gunpowder.  Its  grains  are  of  various 
sizes,  but  have  no  definite  shape.  It  is  mixed  with  another  dirty-white  sand, 
the  grains  of  which  are  much  finer.  .  .  . 

Gregor  found  that  the  black  portion  of  this  sand  had  the  following 
composition: 


Magnetite 
46Vie% 


Silica 


Reddish  Brown  Calx          Loss 
45%  415/ie% 


The  "reddish  brown  calx"  dissolved  in  sulfuric  acid  to  give  a  yellow 
solution  which  became  purple  when  reduced  with  zinc,  tin,  or  iron,  and 
when  the  pulverized  mineral  was  fused  with  powdered  charcoal,  a  purple 
slag  was  formed. 


548  DISCOVERY  OF  THE  ELEMENTS 

Mr.  Gregor  modestly  stated  that  his  paper  was  not  a  complete  in- 
vestigation, but  merely  a  record  of  disconnected  facts,  the  interpretation 
of  which  he  would  leave  to  more  skilful  workers  and  keener  philosophers 
than  himself.  His  friend,  John  Hawkins,  to  whom  he  showed  the  black 
sand,  agreed  that  it  must  be  a  new  mineral. 

The  opinion  of  a  man  so  distinguished  in  mineralogy  [said  Mr.  Gregor], 
together  with  the  extraordinary  properties  of  the  sand,  led  me  to  believe  that 
it  must  contain  a  new  metaUic  substance.  In  order  to  distinguish  it  from  others, 
I  have  ventured  to  give  it  a  name  derived  from  the  region  where  it  was  found- 
namely,  the  Menachan  parish-and  therefore  the  metal  might  be  called 
menachanite. 

He  cautiously  added  that  perhaps  the  researches  of  other  chemists  might 
some  day  explain  the  unusual  properties  of  the  mineral  and  "rob  it  of  its 
novelty."  His  many  duties  unfortunately  prevented  him  from  continuing 
the  investigation  (5)  of  this  black  magnetic  sand  now  known  as  ilmenite, 
FeTiO3.  Strangely  enough,  his  announcement  did  not  attract  much 
attention,  and  thus  titanium,  like  tellurium,  was  quickly  forgotten. 

William  Gregor  died  at  Creed  in  the  summer  of  1817,  after  prolonged 
suffering  with  tuberculosis  (47).  Thomas  Thomson  once  said  of  him: 

Mr.  Gregor  of  Cornwall  was  an  accurate  man,  and  attended  only  to 
analytical  chemistry;  his  analyses  were  not  numerous,  but  they  were  in  general 
excellent.  Unfortunately  the  science  was  deprived  of  his  services  by  a  pre- 
mature death  (ft). 

Mr.  Gregor's  intimate  friend,  the  Reverend  J.  Trist  of  Very  an,  mentioned 
the  exemplary  manner  in  which  he  had  fulfilled  all  the  duties  of  his 
Christian  pastorate,  "dispensing  to  his  neighbors  both  spiritual  and  tem- 
poral benefits,  and  enlivening  the  society  of  his  friends  by  his  cheerful  and 
instructive  conversation"  (2). 

The  reader  will  recall  how  the  honored  chemist  Martin  Heinrich  Klap- 
roth  resurrected  tellurium,  giving  full  credit  to  the  original  discoverer, 
Miiller  von  Reichenstein.  After  Mr.  Gregor's  discovery  had  likewise  fallen 
into  oblivion,  Klaproth  again  came  to  the  rescue.  In  1795  he  separated 
what  seemed  to  be  a  new  oxide  from  a  specimen  of  red  schorl,  or  rutile, 
found  in  Boinik,  Hungary,  and  presented  to  him  by  Count  Wiirben  of 
Vienna  (7,  8).  However,  since  this  oxide  bore  such  a  close  resemblance 
to  the  one  previously  described  by  Mr.  Gregor,  Klaproth  analyzed  a 
specimen  of  menachanite,  or  "iron-shot  titanite  from  Cornwall,"  as  he  pre- 
ferred to  call  it,  for  comparison  ( 21 ) : 

Within  a  few  years  [said  he]  a  fossil  has  been  brought  into  notice  by 
the  name  of  Menachanite,  which  has  been  found  in  the  parish  of  Menachan., 
in  Cornwall,  and  consists  of  grey-black,  sand-like  grains,  obeying  the  magnet. 
Mr.  M'Gregor,  of  Menachan,  who  dedicates  his  study  to  mineralogical  chem- 


ELEMENTS  ISOLATED  WITH  THE  AID  OF  K  AND  NA  549 

istry,  has  given  not  only  the  first  information  of  this  fossil,  but  also  a  full 
narrative  of  his  chemical  researches  concerning  it.  The  chief  result  of  these 
is,  that  menachanite  has  for  its  constituent  parts  iron,  and  a  peculiar  metallic 
oxyd  of  an  unknown  nature.  By  the  following  examination  it  will  appear 
that  this  substance,  which,  besides  iron,  forms  the  second  chief  component 
principle  of  menachanite,  is  precisely  the  very  same  which  constitutes  the 
Hungarian  red  schorl;  namely,  oxyd  of  titanium.  With  this  opinion  also,  most 
of  the  phenomena  noted  down  by  M'Gregor,  in  his  operations  with  mena- 
chanite, agree. 

Klaproth  gave  the  following  curious  reason  for  preferring  to  call 
the  new  element  titanium: 

Whenever  [said  he]  no  name  can  be  found  for  a  new  fossil  which  indicates 
its  peculiar  and  characteristic  properties  (in  which  situation  I  find  myself  at 
present),  I  think  it  best  to  choose  such  a  denomination  as  means  nothing  oi 
itself,  and  thus  can  give  no  rise  to  any  erroneous  ideas.  In  consequence  of 
this,  as  I  did  in  the  case  of  uranium,  I  shall  borrow  the  name  for  this  metallic 
substance  from  mythology,  and  in  particular  from  the  Titans,  the  first  sons 
of  the  earth.  I  therefore  call  this  new  metallic  genus  TITANIUM  (8,  9) . 

Other  Sources  of  Titanium.  Berzelius  once  said  that  the  poet  Goethe 
"had  a  love  for  the  minerals  containing  titanium  and  had  a  collection 
of  them,  in  so  far  as  possible,  from  all  known  localities  where  they  occur. 
When  I  showed  him  how  easily  titanium  is  demonstrated  by  a  beautiful 
reaction,  he  lamented  feelingly  that  his  years  now  prevented  him  from 
perfecting  himself  in  the  use  of  the  blowpipe"  (53). 

Klaproth  found  that  the  mineral  which  Professor  Hunger  discovered 
in  1794,  and  which  crystallized  in  small  quadrangular  rhombic  columns, 
was  a  calcium  titanium  silicate,  titanite.  It  is  also  known  as  sphene  and 
has  the  composition  CaTiSiO5.  Although  titanium  was  once  incorrectly 
thought  of  as  a  rare  element,  it  is  widely  distributed  in  nature.  6f  800 
igneous  rocks  analyzed  by  the  United  States  Geological  Survey,  784  con- 
tained titanium.  While  serving  as  chemist  on  the  Virginia  Geological 
Survey,  W.  M.  Thornton,  Jr.,  obtained  a  positive  test  for  it  in  every  silicate 
he  analyzed  (23}. 

Titanium  in  Plants  and  Animals.  In  1896  C.  E.  Wait  found  large 
amounts  of  titanium  in  the  ashes  of  bituminous  and  anthracite  coals,  oak 
wood,  and  apple  and  pear  wood  (23,  57).  L.  G.  Willis,  in  his  bibliog- 
raphy on  the  minor  elements  in  plant  and  animal  nutrition,  gave  several 
references  to  the  presence  of  small  amounts  of  titanium  in  soils,  in  plants, 
and  in  the  human  body  (58). 

Klaproth,  Vauquelin,  Heinrich  Rose  (22),  and  others  tried  in  vain  to 
isolate  the  metal.  In  1822  Dr.  W.  H.  WoUaston  thought  he  had  found 
it  in  the  form  of  minute  cubic  crystals  in  the  slag  of  the  iron  works  at 


550 


DISCOVERY  OF  THE  ELEMENTS 


Merthyr  Tydvil,  but  F.  Wohler  (18)  showed  in  1849  that  these  were  not 
the  metal  itself  but  a  mixture  of  the  nitride  and  cyanide.  In  1825  Berzelius 
(20)  prepared  some  very  impure  amorphous  titanium  by  reducing  potas- 
sium fluotitanate,  K2TiF63  with  potassium.  Although  the  resulting  black 
powder  gave  a  metallic  streak,  it  was  insoluble  in  hydrofluoric  acid  and 
therefore  could  not  have  contained  much  titanium  metal  (23). 

In  1849  Wohler  and  H.  Sainte-Claire  Deville  attempted  to  prepare 
pure  titanium  by  Berzelius'  method,  but  used  a  closed  crucible  in  order 
to  exclude  air.  When  they  found  that  the  product  thus  obtained  still 
contained  titanium  nitride,  they  heated  boats  containing  potassium  and 
potassium  fluotitanate  in  an  atmosphere  of  hydrogen  and  obtained  a  gray 
powder  which  showed  a  metallic  luster  when  examined  with  a  microscope 
(7,10,18).  Wohler  and  Deville  thought  they  had  the  metal,  but,  in  the 
opinion  of  W.  M.  Thornton,  Jr.  (23),  they  were  still  dealing  with  the 
nitride. 


Sven  Otto  Pettersson,  1848-1941.  Pro- 
fessor of  chemistry  at  the  University  of 
Stockholm  from  1881-1908.  Hydrog- 
rapher  and  oceanographer.  He  colla- 
borated with  Lars  Fredrik  Nilson  in  re- 
searches on  metallic  titanium  and  the 
physical  constants  of  titanium  and  ger- 
manium. He  was  one  of  the  first  chem- 
ists to  support  Svante  Arrhenius  in  his 
views  on  electrolytic  dissociation.  For  a 
discussion  of  his  hydrographic  work  see 
ref.  (69). 


In  1887  Lars  Fredrik  Nilson  and  Otto  Pettersson  finally  prepared  the 
metal  95  per  cent  pure  by  reducing  the  tetrachloride  with  sodium  in  an 
airtight  steel  cylinder  (24,  48).  The  titanium  that  Henri  Moissan  ob- 
tained from  his  electric  furnace  was  free  from  nitrogen  and  silicon  and 
contained  only  2  per  cent  of  carbon  (25). 

In  1910  M.  A.  Hunter  (26)  obtained  the  metal  99.9  per  cent  pure 
by  a  modification  of  Nilson  and  Pettersson's  method  in  which  pure  titanic 
chloride  and  sodium  were  heated  in  a  1000-cc.  machine  steel  bomb  capable 
of  bearing  40,000  kilograms  of  pressure.  The  lid,  which  rested  on  an 


ELEMENTS  ISOLATED  WITH  THE  AID  OF  K  AND  NA 


551 


intervening  gasket  of  soft  copper,  was  securely  held  in  place  by  six- 
braces.  After  the  temperature  had  been  raised  to  low  redness,  the  reac- 
tion took  place  quickly  and  violently.  The  sodium  chloride  was  then 
leached  out  with  water,  leaving  the  pure  titanium. 

The  oxide  titania,  TiO2,  because  of  its  high  refractive  index,  is  used 
in  high-grade  white  pigments  of  great  opacity  and  covering  power.    The 


M.    A.    Hunter's    Bomb    for    preparing    metallic 
titanium. 


Rensselaer  Polytechnic  Institute,  JEng. 
Set.  Series,  No.  1,  p.  6  (1911) 

metal  unites  with  iron  to  form  the  useful  alloy,  ferrotitanium,  which  is 
added  to  molten  steel  to  prevent  formation  of  air  bubbles,  which  would 
form  holes  in  the  finished  castings.  Thus  the  element  that  lay  hidden  for 
centuries  in  the  sand  of  Mr.  Gregor's  parish  is  now  of  direct  benefit  to 
mankind. 


CERIUM 

In  1751  A.  F.  Cronstedt  described  a  heavy  mineral  found  among 
the  copper  and  bismuth  ores  in  the  Bastnas  Mine  at  Riddarhyttan,  Vest- 
manland  (62).  Because  of  its  high  specific  gravity,  this  mineral,  which 
Cronstedt  regarded  as  a  difficultly  reducible  iron  ore,  came  to  be  known 
as  "tungsten  (heavy  stone)  of  Bastnas."  In  1782  Wilhelm  Hisinger,  then 
a  mere  lad  of  fifteen  years,  sent  a  specimen  of  it  to  Scheele  for  analysis. 
In  the  same  year  one  of  the  de  Elhuyar  brothers  from  Spain  also  ana- 
lyzed it  for  practice  when  he  was  studying  under  Torbern  Bergman. 
Although  Bergman  did  not  state  which  of  the  two  brothers  studied  under 
him,  P.  J.  Hjelm  and  L.  von  Crell  both  stated  that  it  was  the  one  who 
afterward  became  director  of  all  the  smelters  of  New  Granada  (63,  64). 
If  this  be  true,  the  analysis  of  the  "heavy  stone  of  Bastnas"  (cerite)  must 
have  been  made  by  Juan  Jose  de  Elhuyar.* 

Scheele  and  de  Elhuyar  proved  independently  that  this  so-called 
"reddish  tungsten"  contains  no  tungsten  (wolfram),  but  neither  of  them 
was  able  to  discover  anything  new  in  it. 

Wilhelm  Rising,  or  Hisinger,  as  he  was  called  after  being  raised  to 

*  See  also  p.  256. 


552 


DISCOVERY  OF  THE  ELEMENTS 


the  nobility,  belonged  to  a  wealthy  Swedish  family  that  owned  the  famous 
Riddarhyttan*  property  in  Vestmanland  and  the  Bastnas  mine,  in  which 
the  mineral  cerite  was  discovered  He  was  born  in  December,  1766,  and 
soon  learned  to  love  the  beautiful  minerals  of  Sweden.  Although  Scheele 
was  unable  to  discover  any  new  metal  in  the  cerite,  this  mistake,  as 
A.  E.  Nordenskiold  said,  is  very  excusable,  for  the  mineral  is  difficult  to 
handle  even  with  modern  methods  of  analysis  (11). 


Statue    of   Carl    Wilhelm   Scheele    at   Koping,    Sweden 


Berzelius  described  cerite  as  follows: 

In  the  iron  mine  at  Bastnas,  now  abandoned,  in  the  vicinity  of  Vestman- 
land, one  finds  a  mineral  of  exceedingly  high  specific  gravity,  called  'lieavy 
stone  of  Bastnas";  that  is  why  Scheele  searched  there,  but  in  vain,  for  tungsten. 
This  mineral  remained  in  oblivion  until  1803,  when  it  was  simultaneously 
examined  by  Klaproth  (44),  by  Hisinger  and  by  myself  (29).  We  found 
in  it  a  new  substance;  Klaproth  called  it  terre  ochroite.  Hisinger  and  I  called 
it  cerous  oxide,  because  there  is  a  higher  oxide,  and  the  two  oxides  give  salts 
of  different  colors  and  properties.  The  root  of  the  name  cerium  was  deduced 
from  that  of  CeresJ  which  Klaproth  changed  to  cerenum,  but  this  name  was 
soon  abandoned.  The  mineral  is  composed  mainly  of  cerous  silicate,  and  for 
this  reason  receives  the  name  of  cente.  Cerium  was  afterward  discovered  in 
minerals  from  other  localities;  for  example,  in  gadolinite,  orthite,  allanite, 
yttrocerite,  cerous  fluoride,  etc."  (12). 

*  The  reader  will  recall  that  Riddarhyttan  was  also  the  birthplace  of  Georg  Brandt, 

the  discoverer  of  cobalt. 

t  The  element  was  named  for  the  planet  Ceres,  which  had  been  recently  discovered  by 

Plazzi. 


ELEMENTS  ISOLATED  WITH  THE  AID  OF  K  AND  NA 


553 


The  main  object  of  Berzelius  and  Hisinger's  analysis  of  cerite  was 
to  search  for  yttria,  which  might  easily  have  escaped  the  attention  of 
Scheele  and  de  Elhuyar  since  it  was  unknown  at  the  time  their  investiga- 
tion was  made  (29).  Although  they  failed  to  find  yttna,  Berzelius  and 
Hisinger  discovered  instead  the  new  earth  ceria.* 


Axel    Fredrik    Cronstedt,t    1722-1765. 

Swedish  chemist  and  mineralogist.  Dis- 
coverer of  nickel  Author  of  a  "System 
of  Mineralogy"  which  was  translated 
into  several  languages  He  called  the 
heavy  mineral  now  known  as  cerite 
"tungsten  of  Bastnas"  Hence  Scheele 
thought  it  might  contain  tungsten.  See 
also  ref.  (52) 


In  his  "Early  Recollections  of  a  Chemist;*  Wohler  gave  a  charming 
picture  of  Hisinger's  home: 

After  a  five  days'  stay  at  Fahlun  [he  wrote]  we  drove  to  Slormskatteberg, 
Hisinger's  estate,  where,  after  a  drive  of  twenty-four  hours,  we  arrived  one 
afternoon,  finding  Berzelius  there.  The  venerable,  genial,  and  most  original 
Hisinger,  so  well  known  through  his  contributions  to  the  geognostic  mineralogy 
and  botany  of  Sweden,  and  through  the  liberality  with  which  he  had  supported 
Berzelius  during  the  commencement  of  his  studies,  lived  here  a  very  rich  man 
(Brukspatron)  on  a  princely  estate,  surrounded  by  magnificent  forests,  gardens, 
and  iron  mines.  We  spent  a  week  here  most  delightfully,  partly  occupied  in 
examining  his  collections,  with  making  blowpipe  tests  of  unknown  minerals, 
and  with  the  reading  aloud  of  my  translation  of  Hisinger's  "Mineral  Geography. 
In  company  with  Berzelius  and  Hisinger,  we  made  an  excursion  a  few  miles 
distant  to  the  mines  of  Riddarhyttan,  among  which  the  Bastnashaft  is  known 

*  In  volumes  9  and  10  of  Nicholson's  Journal  this  paper  was  accredited  to  W  D'Hesin- 

ger  and  J.  B.  Bergelius  [sic\]. 

T  See  Chapter  5,  pp  161-5,  for  biographical  sketch. 


554  DISCOVEBY  OF  THE  ELEMENTS 

as  the  only  locality  for  the  occurrence  of  cente.  At  the  mouth  of  this  mine, 
which  at  that  time  had  already  been  abandoned,  we  collected  in  the  scoichmg 
sun  hundreds  of  the  most  characteristic  specimens  of  cente  and  cenn  [aUanite] 

(23). 

Hisinger  was  indeed  one  of  Sweden's  most  eminent  mineralogists  and 
geologists.  He  died  on  June  28,  1852,  at  the  venerable  age  of  eighty-five 
years. 


,-#,     ::'^  ^  | 

^  r  I  *  -  .  *        ^K, 


Skmnskatteberg,  Vestmanland,  Sweden,  where  Wilhelm  Hisinger  once  lived. 
The  mineral  cente  was  first  found  in  one  of  the  mines  on  his  estate. 


When  Thomas  Thomson  visited  the  Bastnas  Mine  in  1812,  he  wrote: 
"One  of  the  most  remarkable  tracts  in  the  province  of  Westmanland  is 
Riddarhyttan,  a  copper  mine  which  lies  in  the  parish  of  Skinskatteberg, 
about  eighteen  miles  west  and  a  little  south  from  Sala.  .  .  .  The  most 
remarkable  mineral  which  is  found  in  this  mine  is  the  cerite,  a  mineral 
first  noticed  by  Bergman  and  conceived  by  him  to  belong  to  that  called 
tungsten,  and  composed  of  tungstic  acid  and  lime.  Eluyart  [sic]  analysed 
it,  and  showed  that  it  was  not  tungsten.  No  attention  was  paid  to  it 
for  many  years,  till  at  last  it  was  analysed  by  Klaproth  and  by  Hisinger 
and  Berzelius  nearly  about  the  same  time.  Klaproth  discovered  in  it  a 
new  substance  which  he  considered  as  an  earth  and  to  which  he  gave 


ELEMENTS  ISOLATED  WITH  THE  AID  OF  K  AND  NA  555 


Wilhelm  Hisinger,  1766-1852.  Swedish 
mineralogist  and  geologist.  Owner  of  the 
famous  Riddarhytta  mining  property  in 
Vestmanland,  where  cerite  was  discov- 
ered. He  was  one  of  the  first  to  analyze 
the  lithium  mineral  petalite, 


From  Soderbaum's  Jac.  Berzelius  Breu 


William  Francis  Hillebrand,*  1853-1925. 

Chemist  with  the  XL  S,  Geological  Survey, 
later  Chief  Chemist  at  the  Bureau  of 
Standards.  President  of  the  American 
Chemical  Society  in  1906.  Author  of 
"The  Analysis  of  Silicate  and  Carbonate 
Rocks."  He  was  the  first  to  suggest  the 
possibility  of  recovering  potash  from  the 
fumes  from  cement  kilns. 


*  See  ALLEN,  "Pen  Portrait  of  William  Francis  Hillebrand,  1853-1925,"  J,  Chem. 
Educ.,  9,  72-83  (Jan.,  1932). 


556 


DISCOVERY  OF  THE  ELEMENTS 


the  name  ochroita.  Hisinger  and  Berzelius  discovered  in  it  a  new  sub- 
stance which  they  conceived  to  be  a  metallic  oxide,  to  which,  they  gave 
the  name  of  cerium.  Their  results  were  confirmed  by  Vauquelin  and 
have  been  adopted  by  chemists,  .  .  .  Since  the  original  discovery  of 
cerium  in  this  mineral,  it  has  been  found  in  various  other  parts  of  the 
world.  A  mineral  from  Greenland,  to  which  the  name  of  allanite  has  been 
given,  contains  about  the  third  of  its  weight  of  it  .  .  ."  (65) . 

On  one  of  Berzelius'  busy  summer  vacations  at  the  hospitable  home 
of  Assessor  J.  G.  Gahn,  they  discovered  still  another  cerium  mineral,  "For 
two  and  a  half  months,"  said  Berzelius  in  a  letter  to  Dr.  A.  Marcet  on 
October  7,  1814,  "we  occupied  ouiselves  with  nothing  whatever  except 


Thomas  H.  Norton,*  1851-1941.  Pro- 
fessor of  chemistry  at  the  University  of 
Cincinnati.  American  consul  at  Harput, 
Turkey,  at  Smyrna,  and  at  Chemnitz, 
Saxony  Author  of  books  on  dyes,  the 
cottonseed  industry,  potash  production, 
and  the  utilization  of  atmospheric  nitro- 
gen Collaborator  with  W.  F.  Hille- 
brand  in  researches  on  cerium  ( 46,  49 ) . 


mineralogy,  and  I  am  sure  that  few  mineralogists  have  been  more  fortu- 
nate in  their  efforts  than  we.  We  set  out  to  analyze  everything  we  found, 
not  merely  to  learn  their  composition  but  also,  by  means  of  these  analyses, 
to  verify  the  ideas  on  which  my  investigation  of  mineralogy  is  based.  .  .  . 
Behold  our  first  attempt:  a  new  mineral  composed  of  acid  of  fluorspar 
[hydrofluoric  acid],  lime,  yttria,  and  cerium  oxide  [yttrocerite]  .  .  ."  (45}. 
J,  G.  Gahn  in  Sweden  and  N.-L.  Vauquelin  in  France  tried  in  vain  to 
obtain  metallic  cerium.  C.  G.  Mosander  prepared  anhydrous  cerous  chlor- 
ide and  subjected  it  for  a  long  time  to  the  action  of  potassium  vapor.  After 
washing  the  residue  with  cold  alcohol,  he  obtained  a  brown  powder  which, 

*  See  Ind  Eng.  Chem.,  News  Ed.,  13,  318-19  (Aug  10,  1935). 


ELEMENTS  ISOLATED  WITH  THE  AID  OF  K  AND  NA 


557 


when  burnished,  exhibited  a  dark  metallic  luster.    This  cerium  was  far 
from  pure,  however,  for  it  was  badly  contaminated  with  the  oxychloride 
Impure  cerium  was  also  prepared  by  Wohler,    W.  F.  Hillebrand  and  T. 
H.  Norton  (27)  succeeded  in  1875  in  preparing  the  metal  in  a  coherent 
form  by  electrolyzing  fused  cerous  chloride.     In  1911  Dr.  Alcan  Hirsch 


From  "Industry  in  Sweden"  Federation  of  Swedish  Industries 

Mine  Head-Frame  at  Riddarhyttan.     The  mineral  cerite 
was  discovered  there  in  1751  by  A.  F   Cronstedt.    Georg 
Brandt,  the  discoverer  of  cobalt,  was  born  at  Riddar- 
hyttan. 


(30)  made  some  electrolytic  cerium  containing  only  two  per  cent  of 
impurities  (iron,  cerium  oxide,  and  cerium  carbide).  The  metal  was 
purified  by  amalgamating  it  and  distilling  off  the  mercury  in  an  evacuated 
quartz  tube  lined  with  magnesia.  This  elaborate  investigation  required 
more  than  three  years  of  work  at  the  University  of  Wisconsin. 


558  DISCOVERY  OF  THE  ELEMENTS 

Cerium  forms  with  iron  a  peculiar  pyrophoric  alloy  which,  when 
struck,  emits  showers  of  sparks,  and  which  is  used  somewhat  in  the  manu- 
facture of  automatic  gas-lighters  (28). 

Cerium  in  Plants  and  Animals.  Professor  Alfonso  Cossa,  finding  the 
rare  earths  of  the  ceria  series  to  be  present  in  many  apatites,  and  realizing 
the  close  association  in  nature  between  these  earths  and  calcium  and 
phosphorus,  tested  for  them  and  detected  their  presence  in  bone  (66). 
He  also  detected  them  in  the  ash  of  barley,  beech  wood,  and  tobacco. 
With  the  aid  of  C.  Schiapparelli  and  G.  Peroni  of  the  University  of  Turin, 
he  demonstrated  their  presence  in  human  urine  (66,  67,  68). 

THORIUM 

While  analyzing  one  of  the  rare  minerals  from  the  Falun  district, 
Berzelius  found  in  1815  a  substance  that  he  believed  to  be  the  oxide  of  a 
new  metal  which  he  named  thorium  in  honor  of  the  ancient  Scandinavian 
god,  Thor.  Ten  years  later  he  himself  found  that  this  substance  was  not 
a  new  earth,  but  simply  yttrium  phosphate.  He  evidently  liked  the  name 
thorium,  however,  for  when  in  1829  he  really  did  discover  a  new  element, 
he  christened  it  with  the  same  name  (45). 

In  his  account  of  the  discovery,  Berzelius  wrote: 

The  mineral  on  which  I  made  the  following  experiments  is  found 
in  the  syenite  on  the  island  of  Lovo  near  Brevig,  Norway.  It  was  discovered 
by  the  pastor  Esmarck,  son  of  Jens  Esmarck,  famous  professor  at  the  University 
of  Chrisuania.  It  is  the  latter  who  sent  me  a  specimen,  asking  me  to  examine 
it,  because,  on  account  of  its  high  specific  gravity,  he  believed  it  to  be  the  earth 
of  tantalum.  This  mineral  is  black,  with  no  indication  of  crystalline  form  or 
texture,  and  looks  exactly  like  gadolinite  from  Ytterby,  the  exterior  presents 
sometimes  a  thin  rust-colored  surface  layer  (12) . 

After  a  visit  to  Professor  Jens  Esmark,  Edward  Daniel  Clarke  once 
wrote,  "There  is  a  Public  seminary  at  Kongsberg,  in  which  Lectures  on 
Mineralogy  are  delivered  by  Professor  Esmark,  who  is  also  one  of  the 
Assessors,  and  the  most  scientific  mineralogist,  perhaps,  in  all  Europe. 
This  gentleman  is  well  known  in  all  Foreign  Academies  for  the  works 
which  he  has  published.  He  has  done  more  towards  the  overthrow  of 
the  wild  systems  of  the  Plutonists  than  even  Werner  himself.  .  .  .  Pro- 
fessor Esmark  conducted  us  to  the  grand  chamber  of  the  Kongsberg 
Academy,  where  we  saw  a  collection  of  minerals,  in  beautiful  order,  and 
most  scientifically  arranged.  .  .  .  From  him  we  learned  that  the  School 
of  this  Academy  is  a  Royal  Institution  for  the  instruction  of  the  children  of 
the  miners,  in  mineralogy,  chemistry,  physic,  mathematics,  and  other 
branches  of  science.  There  are  three  Professors,  among  whom  Professor 


ELEMENTS  ISOLATED  WITH  THE  AID  OF  K  AND  NA  559 

Esmark  holds  the  mineralogical  and  geological  department.  Any  of  the 
miners  or  children  of  the  miners  may  attend  this  institution.  Two  days 
111  every  week  and  two  hours  in  each  day  are  dedicated  to  the  instruction 
of  the  miners  and  all  other  persons  who  choose  to  attend.  For  these 
lectures,  no  payment  whatsoever  is  required"  (59). 

The  discoverer  of  the  black  mineral  sent  to  Berzelius  was  Professor 
Esmark's  son,  the  Reverend  Hans  Morten  Thrane  Esmark  (1801-1882), 
who  had  acquired  a  lifelong  interest  in  mineralogy,  geology,  and  chemis- 
try under  his  father's  inspiring  guidance.  During  his  long  pastorate  in 
Brevik  he  studied  the  minerals  of  Langesund  Fjord  and  Bamle  and  near 
Krager0,  corresponded  with  scientists  in  other  countries,  and  sent  them 
specimens  of  minerals  for  their  researches.  He  also  communicated  his 
enthusiasm  for  science  to  his  children  Axel  Thrane  Esmark,  a  mineral 
collector  like  his  father  and  grandfather,  and  Birgitte  Elise  Esmark,  who 
became  a  great  philanthropist  and  an  authority  on  rnollusks  (50). 

Although  the  mineral  which  H.  M.  T.  Esmark  discovered  looked  a 
great  deal  like  gadolinite,  his  father  believed  it  to  be  new,  possibly  a  kind 
of  tantalite.  Berzelius'  analysis  of  it  proved  it  to  be  a  silicate  of  a  new 
metal,  which  he  named  thorium  (50,  60).  Although  Pastor  Esmark 
wished  to  name  the  mineral  berzelite,  Berzelius  preferred  the  shorter  name 
thorite  (45). 

Paulin  Louyet,  in  his  eulogy  of  Berzelius,  quoted  the  Scottish  agri- 
cultural chemist  James  Finlay  Weir  Johnston,  who  visited  Stockholm  in 
1829  (the  year  in  which  thorium  was  discovered)  and  afterward  wrote 
a  description  of  Berzelius  and  his  laboratory.  The  visitor/*  said  Johnston, 
"will  recognize  from  various  utensils  in  the  first  room  that  it  is  part  of  a 
chemical  laboratory.  If  he  be  neither  a  chemist  nor  even  an  amateur,  and 
be  his  sense  of  smell  ever  so  delicate,  he  need  not  fear  those  emanations 
which,  in  most  laboratories,  affect  so  painfully  the  organs  of  respiration. 
Here  a  system  of  ventilation,  planned  with  the  greatest  care,  makes  them 
disappear  immediately.  At  his  right  he  will  see,  near  the  window,  a  care- 
fully adjusted  trough  of  mercury,  gleaming  in  the  sun.  .  .  .  After  having 
glanced  at  the  blowpipe,  the  large  lamp,  and  all  the  objects  near  it,  he 
will  come  to  the  sandbath.  He  will  look  in  vain  for  furnaces  of  brick  ov 
stone  .  .  .  they  are  useless  in  the  delicate  operations  of  analysis.  .  ,  . 

"In  the  second  room,"  continued  Johnston.,  "the  first  object  one  notices 
is  a  glass  case  standing  on  a  table.  It  is  the  balance.  How  much  light 
this  fragile,  simple  instrument  has  shed  on  the  natural  sciences!  How 
many  phenomena  it  has  explained!  How  many  hidden  truths  it  has 
revealed!  Who  could  enumerate  the  discussions  it  has  ended,  the  hypo- 
theses it  has  destroyed!  Who,  in  former  times,  would  have  believed  that 
the  determination  of  abstract  truths  and  the  development  of  the  laws  of 
nature  would  depend  on  the  oscillations  of  this  moving  beam!  But 


560      DISCOVERY   OF  THE   ELEMENTS 

consider  this  balance  attentively,  for  it  has  rendered  great  services  to 
science,  and  its  modifications  have  contributed  in  no  slight  degree.  This 
manner  of  raising  the  beam  and  the  pans  and  keeping  them  at  rest  is  due 
to  the  late  Assessor  Gahn,  whose  skill  at  this  kind  of  work  was  well  known. 
Not  far  from  there  are  the  little  lead  weights  which  are  the  exact  counter- 
poises, or  tares,  of  all  the  crucibles  and  small  platinum  utensils  in  the 
laboratory,  so  that  each  of  them  can  be  balanced  in  an  instant.  .  .  . 

"Berzelius  is  always  busy,"  said  Johnston.  "He  works  twelve  to 
fourteen  hours  every  day.  But  in  spite  of  all  he  has  done  for  experimental 
chemistry,  one  must  not  think  that  he  works  without  respite  in  his  labora- 
tory. Often,  when  he  is  composing,  he  stops  for  months  at  a  time.  If, 
during  his  writing,  he  comes  across  some  passage  which  seems  obscure  to 
him,  he  lays  down  his  pen,  goes  into  his  laboratory,  and  carries  out  new 
researches.  .  ,  . 

"Everything  in  Berzelius's  laboiatory,"  said  Johnston,  "is  conspicu- 
ously clean  and  in  admirable  order;  everything  is  in  its  place,  ready  for 
immediate  use.  .  .  .  He  also  uses  many  ingenious  machines  which 
facilitate  or  shorten  his  operations,  the  invention  of  which  he  attributes 
to  Assessor  Gahn.  But  many  of  them  have  been  made  by  himself,  for 
he  turns  or  constructs  those  which  are  of  wood"  (61). 

Thorium,  like  the  other  metals  of  this  group,  is  isolated  with  great 
difficulty.  Berzelius  prepared  the  impure  metal  by  heating  a  mixture  of 
potassium  and  potassium  thorium  fluoride  in  a  glass  tube.  D.  Lely,  Jr., 
and  L.  Hamburger  prepared  it  99  per  cent  pure  by  distilling  sodium  and 
thorium  chloride  into  an  exlmisted  steel  cylinder  and  also  succeeded  in 
obtaining  it  as  a  coherent  metal  (9,  41 ).  It  is  interesting  to  note  that  all 
four  of  the  elements  of  this  group,  titanium,  cerium,  zirconium,  and 
thorium.,  were  isolated  with  the  aid  of  the  alkali  metals  discovered  by  Sir 
Humphry  Davy, 

In  1898  Mme.  Curie  in  Paris  and  Professor  G,  C.  Schmidt  at  the  Uni- 
versity of  Minister,  working  independently,  found  that  thorium,  like 
uranium,  is  radioactive  (43).  This  discovery  opened  up  a  vast  new  field 
of  research  as  a  result  of  which  thorium  is  now  known  to  be  the  parent 
substance  of  an  entire  series  of  radioactive  elements.  The  story  of  their 
discovery  will  be  reserved,  however,  for  a  later  chapter. 

LITERATURE  CITED 

( 1 )      KLAPROTH,  M    H.,  "Ueber  die  vorgegebene  Reduktion  der  einfachen  Erden,** 

Crett'sAnn,  15,  119  (1791). 
(2}     "Biographical  notice  o£  the  Rev,  William  Gregor,"  Annals  of  Phil,   [1],  11, 

112-4  (Feb.,  1818). 
(3)     SODERBAUM,  H  G,,  "Jac.  Berzelius  Brev,"  Vol.  3,  part  6,  Alnaqvist  and  Wiksells, 

Upsala,  1912-1914,  p.  47.    Letter  of  Berzelius  to  Thomson,  Autumn,  1816. 


ELEMENTS  ISOLATED  WITH  THE  AID  OF  K  AND  NA 

(4)  POGGENDORFF,     J.      C,     "Biograpliisch-Litcransches      Handworterbuch     ziir 

Geschichte  der  exakten  Wissenschaften,"  6  \ols.,  Verlag  Chernie,   Leipzig 
and  Berlin,  1863-1937.     Article  on  Gregor 

(5)  GREGOR,  W.,  "Beobachtungen  und  Versuche  uber  den  Menakanite,  einen  in 

Cornwall  gefundenen  magnetischen  Sand,"  CrelTs  Ann  ,  15,  40-54,  103-19 
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(6)  THOMSON,  THOMAS,  "History  of  Chemistry,"  Vol.   2,  Colburn   and  Bentley, 

London,  1831,  p.  231 

(7)  JAGNAUX,  R,  "Histoire  de  la  Chnnie,"  Vol    2,  Baudry  et  Cie.,  Pans,   1891, 

pp  339-40. 

(8}     KLAFROTH,  M.  H.,  "Analytical  Essays  towards  Promoting  die  Chemical  Knowl- 
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8.    Articles  on  Titanium,  Zirconium,  and  Thorium 

(10)  WOHLER,  F  ,  "Sur  le  titane,"  letter  to  Pelouze,  Compt  rend.,  29,  505  (Nov.  5, 
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(11}  NORDENSKIOLD,  A.  E.,  "Scheeles  nachgelassene  Bnefe  und  Aufzeichnungen," 
Norstedt  &  Soner,  Stockholm,  1892,  p.  351. 

(12)  JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  ref   (7),  Vol  2,  pp.  195-9, 

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Am  Chemist,  6,  131  (Oct.,  1875);  "Jugend-Ennnenmgen  emes  Chenukers," 
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(14)  Revelation  21:  20. 

(15)  JAGNAUX,  R ,  "Histoire  de  la  Chimie/'  ref.  (7),  Vol.  2,  p.  176. 

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Communicated  by  Chas.  Hatchett. 

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(Jan,  1823). 

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262  pp. 

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562  DISCOVERY   OF   THE   ELEMENTS 

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(Dec.,  1804);  10,  10-2  (Jan?  1805);  J.  J.  BERZELIUS,  "Analyse  de  la  gado- 
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Eng,  9,540-4  (Get,  1911) 

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Ann  chim.  phys  f  [1],  1,  6  (1789). 

(32)  KXAPROTH,  M.  H.,  "Analytical  Essays  towards  Promoting  the  Chemical  Knowl- 

edge of  Mineral  Substances,"  ref   (8),  pp.  175-94. 

(33)  Ibid.,  pp.  195-9. 

(34)  DE  MORVEAU,  G.,  "Sur  THyacinte  de  France,  congenere  a  celle  de  Ceylan,  et 

sur  la  nouvelle  terre  qui  entre  dans  sa  composition,"  Ann.  chim.  phys.,  [1], 
21,  72-95  (Jan.,  1797). 

(35)  "Extrait  (Tun  memoire  du  Cit  Vauquelin,  contenant  Tanalyse  comparative  des 

Hyacinthes  de  Ceylan  et  d'Expailly,  et  Texpose  de  quelques-unes  des  pro- 
prietes  de  la  terre  qu'elles  conferment,"  ibid.,  [1],  22,  179-210  (May,  1797). 

( 36 )  "Extrait  d'une  lettre  de  M  Berzelius  a  M.  Dulong/'  ibid.,  [2],  26,  43  ( 1824 ) . 

(37)  VENABLE,  F.  P.,  "Zirconium  and  Its  Compounds,"  Chem.  Catalog  Co,  New 

York  City,  1922,  173  pp. 

(38)  WEISS,  L.  and  E.  NAUMANN,  "Darstellung  und  Untersuchung  reguhnischen, 

Zirkoniums,"  2.  anorg.  Chem,  65,  248-78  (Jan,  8,  1910). 

(39)  WET>EKTND,  E.  and  LEWIS,  "Studien  iiber  das  elementare  Zirkonmm/'  Ann., 

371,  366-87  (Heft  3,  1910),  E.  WEDEKIND,  Ann,  395,  149-94  (Heft  2, 
1912). 

( 40)  MOISSAN,  H,,  "Sur  la  volatilisation  de  la  sihce  et  de  la  zircone  et  sur  la  reduction 

de  ces  composes  par  le  charbon,"  Compt  rend ,  116,  1222-4  (May  29,  1893). 

( 41 )  LELY,  D   and  L.  HAMBURGER,  "Herstellung  der  Elemente  Thorium,  Uran,  Zir- 

kon,  und  Titan,"  Z  anorg  Chem.,  87,  209-28  (May  26,  1914). 

(42)  VENABLE,  F.  P.,  "Zirconium  and  Its  Compounds,"  ref.  (37),  pp.  126-32. 

(43)  "Classic  of  science:    Radioactive  substances  by  Mme  Cune,"  ScL  News  Letter 

14, 137-8  (Sept.  1,1928). 

(44)  "Classic  of  science:    Account  of  experiments  made  on  a  mineral  called  cente, 

and  on  the  particular  substance  which  it  contains,  and  which  has  been  con- 
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(45)  SODEEBAUM.,  H.  G.,  "Jac.  Berzelius  levnadsteckning,"  Vol.  2,  Almqvist  &  Wik- 

sells  Boktryckeri  A.-B  ,  Upsala,  1929-31,  pp,  66-8,  501-7,  524-6 

(46)  AJSTON.,  "Thomas  H.  Norton  receives  Lavoisier  medal,"  Ind.  Eng.  Chem.3  News 

Ed.,  15,  542  (Dec.  20,  1937). 

(47)  "Dictionary  of  National  Biography,"  Vol    23,  Smith,  Elder  &  Co,  London, 

1890-91,  pp  89-90.    Article  on  Gregor  by  G.  C.  Boase. 

(48)  VON  EUILEB,  HANS,  "Sven  Otto  Pettersson.     In  memoriam,"  Svensk  Kemisk 

Tidsknft,  53,  28-32  (Jan.,  1941). 

(49)  "Necrology.    Thomas  H.  Norton,"  Ind.  Eng  Chem  ,  News  Ed.,  19,  1474  (Dec 

25,  1941). 

(50)  BULL,  E.  and  E.  JANSEN,  "Norsk  Biografislc  Leksikon,"  Vol.  3.  H.  Aschenhoug 

and  Co.,  Oslo,  1926,  pp.  595-6     Articles  on  the  Esmark  family. 

(51 )  BARTOW,  VIRGINIA,  "W,  F.  Hillebrand  and  some  early  letters/*  /.  Chem.  Educ., 

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(52)  BARTOW,  VIRGINIA,  "Axel  Frednk  Cronstedt,"  ibid.,  30,  247-52  (May,  1953) 

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Williams  &  Wilkins  Co.,  Baltimore,  Md.,  1934,  p.  114. 


ELEMENTS  ISOLATED  WITH  THE  AID  OF  K  AND  NA  563 

(54)  WIEGLEB,  J.  C,5  "Chemische  Unteisuchung  der  Zirkonen  aiis  Zellon,"  CreWs 

Ann,  8,  139-43  (1787). 

( 55)  KLAPROTH,  M.  H.,  Ref  ( 8 ),  pp.  175-217. 

(56)  KXAFROTH,  M.  H.  and  F.  WOLFF,  "Dictionnaire  de  chunie,"  Vol.  4,  Kloster- 

mann  Fils,  Pans,  1811,  p   547. 

(57)  WAIT,  C.  E.,  "The  occurrence  of  titanium,"  J.  Am    Chem.  Soc.,   18,  402-4 

(Apr.,  1896). 

(58)  WILLIS,  L.  G    "Bibliography  of  References  to  the  Literature  on  the  Minor 

Elements   and  Their  Relation   to   Plant   and   Animal  Nutrition/'   3rd   ed  , 
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(59)  CLARKE,  E.  D  ,  "Travels  m  Various  Countries  of  Europe,  Asia,  and  Africa,"  Vol 

10,  T  Cadell,  London,  1824,  pp.  441-3. 

(60)  WALLACH,  CX,  "Briefwechsel  zwischen  J.  Berzehus  und  F.  Wohler,"  Vol    1, 

Wilhelm  Engelrnann,  Leipzig,  1901,  p.  252.    Letter  of  Berzehus  to  Wohler, 
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( 61 )  LOUYET,  PAULIN,  "Nonce  sur  la  vie  et  les  travaux  de  J.-J.  Berzelius,"  Annuaire 

de  VAcad   Roy.  des  Sciences,  des  Lettres,  et  des  Beaux-Arts  de  Belgique, 
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(62)  CRONSTEDT,  A.   F.,   "Ron   och  forsok   gjorde   med   trenne   jarnmalms  arter," 

K.  Vet  Acad.  Handl ,  12,  226-32  (July,  Aug ,  Sept.,  1751). 

(63]     HJELM,  P.  J.,  "Aminnelse-tal  ofver  .  .  .  Torbern  Bergman,"  J.  G.  Lange,  Stock- 
holm, 17863  p    86. 

(64)  CRELL,  L    VON?  "Zum  Andenken  Torbern  Bergmans,"  Crell's  Ann.,  7,  74^96 

(1787). 

(65)  THOMSON,  THOMAS,  "Travels  through  Sweden  in  the  Autumn  of  1812,"  Robert 

Baldwin,  London,  1813,  pp.  193-4,  228-9,  241-4 

(66)  COSSA,  ALFONSO,  "Sulla  difrusione  del  cerio,  del  lantano  e  del  didymio,"  Gazz. 

chim  ital,  9,  118-40  (1879);  10,  465-6  (1880). 

(67)  SCHIAPPARELLI,  C.  and  G    PERON^  "Di  alcum  nuovi  component!  dell'unna 

umana  normale,"  Gazz.  chim,  ital.,  10,  390-2  (1880). 

(68)  PROVENZAL,  GIULIO,  "Profili  Bio-Bibliografici  di  Chimici  Italiani.     Sec.  XV- 

Sec.    XIX,"    Istituto    Nazionale    Medico    Farmacologico    "Serono/*    Rome, 
1937,  pp.  221-9. 

( 63 )  CARSON,  RACHEL  L ,  "The  Sea  Around  Us,"  Mentor  Book  published  by  the 

New  American  Library,  New  York,  1954,  pp.  136-41. 


From  "La  Science 

Dept.  Public  Instruction,  Paris 


Rene-Just  Hatty,  1743-1822.  French  mineralogist.  He  deduced 
the  fundamental  laws  of  crystallography,  and  explained  cleavage 
by  postulating  that  a  crystal  is  built  up  of  small  similar  parallele- 
pipeds. He  was  the  first  to  recognize  that  beiyl  and  the  emerald 
are  geometrically  identical,  Vauquelin's  proof  of  their  chemical 
identity,  made  at  the  suggestion  of  Haxiy,  led  to  the  discovery  of  the 
element  beryllium.  See  also  ref.  (164), 


Aber  neue  Phaenomena  zu  erklaren,  dieses  macht 
meine  Sorgen  aits,  und  wie  froh  1st  der  Forscher, 
wenn  er  das  so  fieissig  Gesuchte  findet,  eine 
Ergotzung  wobei  das  Herz  lacht  (l).—"To  explain 
new  phenomena,  that  is  my  task;  and  how  happy 
is  the  scientist  when  he  finds  what  he  so  diligently 
sought,  a  pleasure  that  gladdens  the  heart" 


22 

Other  elements  isolated  with  the  aid  of 
potassium  and  sodium 


When  the  Abbe  Hauy  pointed  out  the  dose  similarity  and 
probable  identity  of  beryl  and  the  emerald,  Vauquelin  analyzed 
them  carefully,  and  found  in  1798  that  they  are  indeed  identical, 
and  that  they  contain  a  new  earth,  which  he  named  glucina,  but 
ivhich  is  now  known  as  beryllia  The  metal  was  isolated  thirtij 
years  later  by  Wohler  and  Bussy  independently.  Boron  was 
isolated  in  1808  by  Gay-Lussac  and  Thenard  in  France  and  by 
Davy  in  England  by  reduction  of  boric  acid  with  potassium. 
Although  amorphous  silicon  was  prepared  by  Berzelius  in  1824, 
the  crystalline  form  of  it  was  not  obtained  until  about  thirty 
years  later,  when  Henri  Sainte-Clarie  Deville  prepared  it  by  an 
electrolytic  method  Aluminum  was  isolated  in  1825  by  the 
Danish  physicist,  Oersted,  and  two  years  later  Wohler  prepared 
it  by  a  better  method.  Successful  commercial  processes  for  the 
manufacture  of  this  important  metal  were  perfected  by  Henri 
Samte-Claue  Deville,  by  Charles  Martin  Hall,  and  by  Dr.  Paul 
L.  T.  Heroult. 


BERYLLIUM 


B, 


'eryl  was  probably  not  used  in  Egypt  before  Ptolemaic  times 
(87).  A.  Lucas  stated  that  the  mines  in  the  Red  Sea  hills,  which  were 
mentioned  by  Strabo  and  Pliny  the  Elder,  were  probably  the  only  source 
of  beryl  in  ancient  times  (87).  In  1817  F.  Cailliaud  discovered  the 
emerald  mines  near  Mt  Zabara  "nearly  in  the  same  state  in  which  they 
had  been  left  by  the  engineers  of  the  Ptolemies,  He  penetrated  into  a 
vast  number  of  excavations  and  subterraneous  canals,  some  of  which  are 
so  deep  that  four  hundred  men  may  work  in  them  at  once.  ...  M.  C. 
himself  set  about  working  the  mines,  and  he  has  presented  six  pounds  of 
emeralds  to  Mahommed  Ali  Pashaw"  (88). 

Pliny  the  Elder  realized  that  beryl  and  the  emerald  are  closely  related 
(56).  "Beryls,  it  is  thought,  are  of  the  same  nature  as  the  smaragdus,  or 
at  least  closely  analogous.  India  produces  them,  and  they  are  rarely  to 

565 


566  DISCOVERY  OF  THE  ELEMENTS 

be  found  elsewhere"  (56).  William  Ridgeway  stated  in  the  "Encyclo- 
paedia Biblica '  that  the  Greeks  and  Romans  executed  some  of  their  finest 
gem  engraving  in  beryl.  The  Stockholm  papyrus,  which  dates  fiom  the 
third  or  fourth  century  A.D.,  gives  several  recipes  for  the  preparation  of 
artificial  beryl  and  emerald  (59). 

In  1590  Father  Jose  de  Acosta  described  the  Peruvian  emeralds. 
"They  have  been  found  in  diverse  partes  of  the  Indies,"  said  he.  "The 
Kings  of  Mexico  didde  much  esteeme  them;  some  did  vse  to  pierce  their 
nosthrils,  and  hang  therein  an  excellent  emerald;  and  they  hung  them  on 
the  visages  of  their  idolles.  The  greatest  store  is  found  in  the  New  King- 
dome  of  Grenada  and  in  Peru,  neere  vnto  Manta  and  Puerto  Viejo.  There 
is  towardes  that  place  a  soile  which  they  call  the  Land  of  Emeraldas,  for 
the  knowledge  they  have  of  aboundance  to  be  there;  and  yet  vnto  this 
day  they  have  not  conquered  that  land.  ...  In  the  fleete,  the  yeare 
one  thousand  five  hundred  eighty  and  seven,  in  the  which  I  came  from 
the  Indies,  they  brought  two  chests  of  emeralds,  every  one  weighing  at 
least  four  arrobas  [1  arroba  =  25  Ibs.],  whereby  we  may  see  the  aboun- 
daunce  they  have.  The  holy  Scripture  commends  these  emeralds  as 
pretious  iewels,  they  number  them  amongst  the  pretious  stones  which 
the  hie  Priest  carried  on  his  Ephod  or  breastplate,  as  those  which  did 
beautifie  the  walles  of  the  heavenly  lerusalem"  (90).  The  term  smaragdus 
as  used  in  the  Bible,  however,  may  have  included  other  green  gems  as 
well  as  the  emerald. 

The  correct  composition  of  beryl  and  the  emerald  was  not  known 
until  the  close  of  the  eighteenth  century,  when  the  Abb6  R.-J.  Hauy 
pointed  out  the  remarkable  similarity  in  crystalline  structure,  hardness, 
and  density  of  a  beryl  from  Limoges  and  an  emerald  from  Peru,  and 
N.-L,  Vauquelin  discovered  that  they  both  contain  as  an  essential  con- 
stituent glucinum,  or  beryllium,  and  that  the  emerald,  except  for  the 
presence  in  it  of  a  little  chromium,  has  the  same  composition  as  the  beryl 
(25,27,91). 

The  latter  wrote  in  1798:  "Klaproth  had  no  sooner  discovered  the 
different  substances  with  which  he  has  enriched  the  science,  but  they 
were  found  in  various  other  bodies;  and  if  I  may  refer  to  my  own 
processes,  it  will  be  seen  that  after  I  had  determined  the  characters  of 
chrome,  first  found  in  the  native  red  lead,  I  easily  recognized  it  in  the 
emerald  and  the  ruby.  The  same  has  happened  with  regard  to  the  earth 
of  the  beryl,  I  have  likewise  detected  it  in  the  emerald;  in  which,  never- 
theless, it  was  overlooked  by  Klaproth  and  myself  in  our  first  analysis;  so 
difficult  it  is  to  be  aware  of  the  presence  of  a  new  substance,  particularly 
when  it  possesses  some  properties  resembling  those  already  known  .  .  ." 
(23). 


ELEMENTS  ISOLATED  WITH  K  AND  NA  567 

At  the  close  of  his  paper  Vauquelin  added:  "I  present  to  the  Insti- 
tute a  certain  quantity  of  this  earth,  and  shall  produce  at  one  of  its  future 
sittings  a  series  of  combinations  formed  with  this  earth  .  .  ."  (23). 

In  speaking  of  the  discovery  of  beryllium  A.-F.  de  Fourcroy  once 
said,  "It  is  to  geometry  that  we  owe  in  some  sort  the  source  of  this  dis- 
covery; it  is  that  [science]  that  furnished  the  first  idea  of  it,  and  we  may 
say  that  without  it  the  knowledge  of  this  new  earth  would  not  have  been 
acquired  for  a  long  time,  since  according  to  the  analysis  of  the  emerald 
by  M.  Klaproth  and  that  of  beryl  by  M.  Bindheim  one  would  not  have 
thought  it  possible  to  recommence  this  work  without  the  strong  analogies 
or  even  almost  perfect  identity  that  Citizen  Hauy  found  for  the  geo- 
metrical properties  between  these  two  stony  fossils"  (5). 

As  a  result  of  his  analysis  of  a  Peruvian  emerald.,  Klaproth  had 
stated  that  this  gem  has  the  following  composition: 

Silica  "Silex"  Alumina,  "Alumine  or  Argil"  Iron  Oxide 

66  25%  31.25%  0,50% 

To  explain  his  extravagance  he  said,  "For  the  specimen  of  emerald  sacri- 
ficed to  this  analytical  process,  I  am  indebted  to  the  liberal  kindness  of 
Prince  Dimitri  Gallitzin,  whose  zeal  for  the  study  of  mineralogy  is  most 
honourably  known"  (22). 

Beryl  had  also  been  analyzed  by  T.  Bergman,  F.  K.  Achard,  J.  J. 
Bindheim,  and  N.-L.  Vauquelin,  and  was  supposed  to  be  a  calcium 
aluminum  silicate  (23).  The  identity  of  beryl  and  the  emerald  was  not 
suspected  until  the  famous  French  mineralogist  the  Abbe*  R.-J.  Hairy 
made  a  careful  study  of  their  crystal  forms  and  physical  properties  and 
was  so  struck  by  the  similarity  of  the  two  minerals  that  he  asked  Vauquelin 
to  analyze  them  chemically. 

Although  the  latter  had  previously  overlooked  the  new  earth  because 
of  its  similarity  to  alumina,  he  found  in  1798  that  the  hydroxide  that 
precipitates  when  caustic  potash  is  added  to  an  acid  solution  of  the  beryl 
does  not  dissolve  in  an  excess  of  the  alkali.  It  also  differs  from  alumina 
in  other  respectss  for  it  forms  no  alum,  it  dissolves  in  ammonium  carbonate, 
and  its  salts  have  a  sweet  taste.  Vauquelin's  paper  read  before  the  French 
Academy  on  "le  26  pluviose  an  VI"  of  the  Revolutionary  Calendar,  or  the 
fifteenth  of  February,  1798  (6,  23),  proved  that,  except  for  a  little 
chromium  in  the  emerald,  the  two  gems  have  the  same  composition  and 
that  they  contain  a  new  earth,  a  sample  of  which  he  presented  to  the 
Academy.  At  the  suggestion  of  the  editors*  of  the  Annales  de  Chimie  et 
de  Physique,  he  called  the  new  earth  glucina,  meaning  sweet.  The 
specimen  of  beryl  that  Vauquelin  analyzed  was  presented  to  him  by 

*  Guyton  de  Morveau,  G.  Monge,  C  -L.  Berthollet,  A.-F.  de  Fourcroy,  A  Seguin,  J.- 
A.-C.  Chaptal,  and  N.-L.  Vauquelin. 


568 


DISCOVERY  OF  THE  ELEMENTS 


"Citizen  Patrin,  whose  zeal  for  the  advancement  of  the  sciences  is  well 
known  to  every  one  of  their  cultivators"  (23). 

Vauquelin  believed  that  Torbern  Bergman's  incorrect  conclusions  as 
to  the  chemical  nature  of  the  beryl  had  been  caused  by  the  unwillingness 
of  his  "active  mind  to  submit  to  the  details  of  experiment/'  Thus  Bergman, 
and  Bindheim  as  well,  had  entrusted  their  analyses  to  young  pupils  who 
were  incapable  of  distinguishing  a  new  substance  when  they  saw  it. 
According  to  Bindheirns  analysis,  the  beryl  consisted  of  64  per  cent  of 
silica,  27  per  cent  of  alumina,  8  per  cent  of  lime,  and  2  per  cent  of  iron 
(total  101  per  cent)  (23). 


Johann  Friedrich  Gmelin,  1748-1804. 
Father  of  Leopold  Gmelin.  Professor  of 
chemistry  at  Tubingen  and  Gottingen 
Famous  chemical  historian.  His  remark- 
able "Geschichte  der  Cherme"  was  pub- 
lished in  1797-99. 


When  Vauquelin  analyzed  a  Peruvian  emerald  (25)  after  his  dis- 
covery of  chromium  and  glucina,  the  results  differed  greatly  from  his 
previous  ones  and  from  those  of  Klaproth.  He  found: 


Silica 

Alumina 

Glucina 

Lime 

Chromium  oxide 

Moisture,  or  other  volatile  matter 


6460 

14.00 

13.00 

256 

3.50 

2QQ 

9966 


J.  F.  Gmelin's  analysis  of  a  Siberian  beryl  soon  confirmed  Vauquelin's 


ELEMENTS  ISOLATED  WITH  K  AND  NA 


569 


conclusions  as  to  the  essential  constituents  of  that  gem,  for  he  found  no 
lime,  but  only  silica,  alumina,  glucina,  and  a  small  amount  of  iron  oxide 
(26). 

Since  yttria,  as  well  as  glucma,  forms  sweet  salts,  Klaproth  preferred 
to  call  the  latter  earth  berylha,  and  it  is  still  known  by  that  name.  Beryl 
and  the  emerald  are  now  known  to  be  a  beryllium  aluminum  silicate 

[Be3Al2(SiO3)6]. 

Metallic  beryllium  was  first  prepared  in  August,  1828,  by  F.  Wbhler 
and  A.-A.-B.  Bussy  independently  by  the  action  of  potassium  on  beryllium 
chloride  (7y  8).  Wohler  placed  alternate  layers  of  the  chloride  and 
flattened  pieces  of  potassium  in  a  platinum  crucible,  wired  the  cover  on 
strongly,  and  heated  the  mixture  with  an  alcohol  lamp.  The  reaction 
began  immediately  and  took  place  with  such  intensity  that  the  crucible 
became  white-hot.  After  cooling  it  thoroughly,  he  opened  it  and  placed 


Hexagonal  Crystals  of  Pure  Beryllium 
prepared  by  P.  Lebeau. 


it  in  a  large  volume  of  water,  whereupon  the  beryllium  separated  out  as 
a  gray-black  powder.  After  washing  this  insoluble  material,  Wohler  saw 
that  it  consisted  of  fine  metallic  particles  which  could  be  burnished  to 
show  a  dark  metallic  luster.  He  did  not  succeed  in  melting  the  beryllium 
(8). 

The  first  person  to  prepare  pure  beryllium  by  an  electrolytic  process 
was  the  French  chemist,  P.  Lebeau  (27,  29).  After  adding  potassium 
or  sodium  fluoride  to  pure  beryllium  fluoride  to  make  it  conduct  the 
current,  he  placed  the  mixture  in  a  nickel  crucible.  After  melting  the 
double  salt  with  a  Bunsen  burner,  he  placed  the  positive  (graphite) 
electrode  in  the  fluoride  mixture  and  connected  the  nickel  crucible  to 
the  negative  side  of  a  battery  of  twenty  amperes  under  eighty  volts  In 
less  than  an  hour  crystals  of  beryllium  were  deposited  on  the  sides  of  the 
crucible.  After  washing  them,  first  with  water  and  then  with  absolute 
alcohol,  and  drying  them  in  a  vacuum  desiccator  containing  phosphorus 
pentoxide,  Lebeau  found  that  they  contained  from  99.5  to  99.8  per  cent 


570 


DISCOVERY  OF  THE  ELEMENTS 


of  beryllium.     This  research  provided  the  data  for  his  thesis  for  the 
doctorate  in  June,  1898. 

Nearly  a  century  after  Wdhler  and  Bussy  liberated  beryllium,  Alfred 
Stock  and  Hans  Goldschmidt  devised  the  first  commercial  process,  in 
which  a  mixture  of  the  fluorides  of  beryllium  and  barium  is  electrolyzed. 
The  molten  beryllium  separates  out  at  the  water-cooled  iron  cathode  (24). 


\  IVIO^  AMI 

GAY-LUSSAC 


iE  DK  L'ACAtftMIE  ROYALE  DE5 
UK  I/mim'T  DK  FRANCE, 


JW 


BOUIE 


Dedication  Page  of  Thenard's  "Traite 
de  Chimie,"  a  five-volume  work. 


Beryllium  in  Plants  and  Animals.  In  1888  F.  Sestini  found  beryllium 
in  land  plants  grown  in  soils  containing  it  (92,  93).  He  found  later  that, 
although  beryllium  may  take  the  place  of  magnesium  as  a  nutrient  for 
wheat,  it  is  not  a  complete  substitute  for  magnesium  in  the  production 
of  seed  (93).  Beryllium  is  occasionally  present  in  bone  (94). 


BORON 

Tincal  (Borax).  Even  in  the  eighteenth  century,  borax  was  believed 
to  be  an  artificial  production  (59,  60).  Caspar  Neumann  (1683—1737) 
said  that  "Borax  is  a  saline  substance.,  of  which  neither  the  origin  nor  the 
component  parts  are  as  yet  known.  It  comes  from  the  East-Indies  in 
little  crystalline  masses.  .  .  .  The  refining  of  Borax  was  formerly 
practised  only  at  Venice,  and  hence  the  refined  Borax  was  called  Venetian; 
but  the  Dutch  are  now  the  only  masters  of  this  manufacture.  Serapio 
calls  the  rough  Borax  as  it  comes  from  the  Indies  linear;  and  the  dealers 
in  this  commodity  still  distinguish  it  by  the  name  Tincar  or  Tincal, 
never  calling  it  Borax  till  it  is  refined"  (95). 

P.-J.  Macquer  (1718-1784)  said  that  "Though  Borax  is  of  great  use 
in  many  chymical  operations,  especially  in  the  fusion  of  metals,  .  .  . 
yet  till  of  late  years  Chymists  were  quite  ignorant  of  its  nature,  as  they 
still  are  of  its  origin;  concerning  which  we  know  nothing  with  certainty., 
but  that  it  comes  rough  from  the  East  Indies  and  is  purified  by  the 
Dutch"  (96). 


ELEMENTS  ISOLATED  WITH  K  AND  NA  571 

Macquer  stated  that  borax  contains  "an  Alkali  like  the  basis  of  Sea- 
salt.  This  Alkali  is  not  perfectly  neutralized  by  the  sedative  salt  [boric 
acid],  which  is  also  contained  in  Borax,  for  its  alkaline  properties  are  so 
perceptible  as  to  have  led  some  Chymists  to  think  that  Borax  was  only 
an  Alkali  of  a  particular  kind"  ( 96 ) . 

In  1772,  however,  the  Swedish  merchant  Johan  Abraham  Grill 
(Abrahamsson)  described  in  volume  thirty-four  of  Vetenskapsacademi- 
ens  Handlingar  a  natural  borax  called  pounxa  sent  him  from  Thibet  by 
Jos.  Vit  Kuo,  a  native  Chinese  Catholic  missionary,  "From  the  report 
of  my  correspondent  Vit.  Kuo,"  said  he,  "it  can  be  inferred  that  the 
pounxa  is  found  in  Thibet,  that  to  obtain  it  one  digs  into  the  ground  to 
the  depth  of  two  yards;  ...  it  positively  cannot  be  made  artificially 
by  heating  the  earth;  it  is  found  already  prepared  by  nature"  (61). 

In  the  same  year  Gustaf  von  Engestrom  analyzed  the  different  lands 
of  pounxa  and  also  two  kinds  of  tincal,  one  from  the  Netherlands  and 
another  which  the  Councilor  of  Mines  Georg  Brandt  ("Bergrath  Brand") 
had  received  from  East  India  (97).  Through  their  connections  with 
the  Swedish  East  India  Company,  von  Engestrom,  Johan  Abraham  Grill, 
and  Peter  Johan  Bladh  were  able  to  obtain  and  analyze  several  minerals 
from  the  Orient,  especially  from  China  (98).  The  results  of  these 
analyses  were  published  in  Vetenskapsacademiens  Handlingar  from  1772 

to  1776. 

Analyses  by  R.  Nasini  and  R.  Grassini  indicated  that  boric  acid 
entered  into  the  composition  of  the  brilliant  coral  red  glazes  on  the 
Aretrne  vases  (first  century  B.C.  to  first  century  A.D.)  excavated  at 
Arezzo  (57,  76).  Because  of  the  seal,  or  impression,  on  the  bottom, 
these  vases  were  known  as  "terra  sigillata  ware."  Paul  Diergart  of  the 
research  staff  of  the  Royal  Porcelain  Works  in  Berlin  questioned  these 
analyses,  however  (58). 

Boric  acid  was  first  prepared  in  1702  by  Willem  Homberg.  He 
was  born  on  January  8,  1652,  at  Batavia  on  the  island  of  Java.  When 
his  father  left  the  service  of  the  Dutch  East  India  Company,  the  family 
settled  in  Amsterdam,  where  young  Wilhelm  (or  Willem)  had  a  much 
better  opportunity  to  study  than  in  the  torrid  climate  of  the  East  Indies, 
After  studying  law  at  Jena  and  Leipzig,  he  was  admitted  to  the  bar  in 
Magdeburg  in  1674.  Soon  becoming  more  interested  in  the  laws  of 
nature  than  in  those  devised  by  man,  he  began  to  devote  much  time  to 
botany,  astronomy,  and  mechanics. 

The  Burgomaster  of  the  city,  Otto  von  Guencke,  was  then  perform- 
ing "the  Magdeburg  miracles"  with  the  evacuated  hemispheres  which 
sixteen  horses  could  not  separate  and  with  his  curious  barometer,  "the 
little  man  who  remained  hidden  in  a  tube  when  the  weather  was  to  be 


572 


DISCOVERY  OF  THE  ELEMENTS 


rainy  and  came  out  when  it  was  to  be  fair"  (62).    These  wonders  still 
further  diverted  Homberg's  attention  from  his  practice  of  law. 

At  Padua  and  Rome,  he  studied  medicine,  optics,  art,  and  music. 
After  further  study  in  France,  he  went  to  England  to  work  with  Robert 
Boyle,  thence  to  the  Netherlands,  where  he  studied  anatomy,  and  finally 
to  Wurttemberg,  where  he  received  the  degree  of  doctor  of  medicine. 
Homberg  then  visited  the  mines  of  Saxony,  Hungary,  and  Bohemia,  and 


RaffaeUo  Nasini,  1854-1931.  Italian 
chemist  who  reported  the  presence  of 
boric  acid  in  the  glazes  of  ancient  Aretine 
vases,  and  studied  the  rare  gases  of  the 
bone  acid  soflaoni,  or  hot  springs,  of  Tus- 
cany In  his  youth  he  assisted  Stanislao 
Caniuzzaro  and  in  later  life  he  collabo 
rated  with  Giacomo  Ciamician 


went  to  Sweden  to  see  the  great  copper  mine  at  Falun.  Although  it  has 
often  been  stated,  on  the  basis  of  Fontenelle's  eulogy,  that  Homberg 
worked  for  a  time  with  Urban  Hiarae  at  the  newly  established  chemical 
laboratory  at  Stockholm,  Sten  Lindroth  found  no  record  of  this  and 
believes  that  Homberg  may  possibly  have  worked  in  Hiarne's  private 
laboratory  before  the  new  laboratory  at  Stockholm  was  established  in 
1683  (85).  When  Homberg  returned  to  Paris,  the  Duke  of  Orleans 
studied  under  him,  caught  his  enthusiasm,  and  equipped  for  him  "the 
most  superb  and  best  furnished  laboratory  Chemistry  had  ever  seen" 
(62). 

In  1702  Homberg  stated  in  the  Memoirs  of  the  Academy  of  Sciences 
at  Paris  that  he  had  heated  borax  with  a  solution  if  iron  vitriol  (ferrous 


ELE1MENTS  ISOLATED  WITH  K  AND  NA  573 

sulfate)  and  sublimed  off  with  the  water  vapor  a  substance  which  he 
called  sel  volatil  narcotique  du  vitriol  ("volatile  sedative  salt  from  the 
vitriol" ) .  Thus  it  is  evident  that  he  must  have  prepared  boric  acid  and 
that  he  believed  that  it  came  from  the  ferrous  sulfate  (63).  He  used 
hot  water  to  extract  the  colcothar  or  residue  which  remained  in  the  retort 
after  distillation  of  Nordhausen  sulfuric  acid,  filtered  the  solution,  and 
mixed  with  it  a  hot  solution  of  borax.  After  evaporating  the  mixture  to 
incipient  crystallization,  he  heated  it  on  a  sandbath,  using  a  cucurbit 
and  alembic.  When  the  liquid  products  of  distillation  ceased  to  drip 
into  the  receiver,  snow-white  platelets  with  a  mother-of-pearl  luster  sub- 
limed in  the  still-head.  By  redistilling  the  aqueous  distillate  eight  or 
ten  times,  Homberg  obtained  a  good  yield  of  the  "sedative  salt"  (63). 

F.  M.  Jaeger  found  in  the  correspondence  of  Elisabeth  Charlotte  of 
Orleans  (1652-1721)  a  firsthand  character  sketch  of  the  discoverer  of 
boric  acid.  "One  cannot  know  Homberg,"  said  she,  "without  admiring 
him  for  his  clear  mind,— not  at  ah1  confused  as  the  highly  educated  usually 
are,  and  not  solemn,  but  always  jolly;  everything  he  knows,  even  the  most 
difficult  arts,  seem  with  him  to  be  a  jest,  as  though  he  were  playing 
tricks  ...  He  has  a  soft  voice,  and  speaks  very  slowly  but  clearly" 
(64). 

During  his  last  illness,  Homberg's  patience  "was  that  of  a  hero  or 
a  saint  A  few  days  before  his  death,"  said  B.  Le  Bovier  de  Fontenelle 
in  his  eulogy,  "he  took  the  liberty  of  writing  to  His  Royal  Highness  the 
Duke  of  Orleans  ...  to  recommend  to  him  all  that  he  had  most  loved, 
the  widow  whom  he  was  about  to  leave  and  the  Academy  of  Sciences. 
His  prayer  for  the  Academy  had  more  success  than  he  would  have  dared 
to  hope;  the  prince  has  reserved  for  himself  alone  the  direct  management 
of  this  Company.  He  treats  our  sciences  like  his  own  domain,  of  which 
he  is  jealous"  (62). 

Willem  Homberg  died  on  the  twenty-fourth  of  September,  1715. 
"Although  he  had  a  weak  constitution,  he  was  most  industrious;  although 
he  lacked  strength,  he  had  courage  to  compensate  for  it.  Besides  a 
prodigious  quantity  of  curious  facts  of  natural  philosophy  collected  in 
his  mind  and  retained  in  his  memory,  he  had  the  qualifications  of  an 
ordinary  scholar  in  history  and  languages.  He  even  knew  Hebrew.  His 
quality  of  mind  is  evident  in  all  his  work:  above  all,  an  ingenious 
attentiveness  which  caused  him  to  make  observations  where  others  saw 
nothing.  .  .  . 

"We  have  already  mentioned  his  complete  freedom  from  ostenta- 
tion," said  Fontenelle.  "He  was  equally  free  from  mystery,  so  common 
among  chemists,  which  is  merely  another  kind  of  ostentation  in  which  one 
conceals  instead  of  displaying.  .  .  .  Although  French  was  always  a 
foreign  language  for  him  and  he  naturally  was  not  rich  in  vocabulary  and 


574 


DISCOVERY  OF  THE  ELEMENTS 


had  continually  to  seaich  for  the  right  word,  he  always  found  it.  No 
one  ever  had  more  gentle  manners  nor  more  sociable  habits.  ...  A 
wholesome,  peaceful  philosophy  made  him  receive  calmly  the  different 
events  of  life,  immune  to  those  agitations  for  which  one  has,  if  one 
wishes,  so  many  occasions"  (62).  Further  information  concerning  Horn- 
berg  may  be  found  in  Professor  Heinrich  Rheinboldfs  book  on  the 
balance  and  weights  in  the  preclassical  epoch  of  chemistry  (82). 


Louis-Jacques  Thenard,  1777-1857.  Pro- 
fessor of  chemistry  at  the  Ecole  Poly- 
technique.  Discoverer  of  hydrogen 
peroxide.  Collaborator  with  Gay-Lussac 
in  his  researches  on  potassium,  boron, 
iodine,  and  chlorine.  He  also  investi- 
gated many  fatty  acids,  esters  and  ethers 


G.  E.  Stahl  showed  in  1723  that  the  "sedative  salt"  could  be  prepared 
by  treating  borax  not  only  with  sulfuric  acid  but  also  with  other  acids 
(99,  100).  Louis  Lemery,  son  of  Homberg's  friend  Nicolas  Lemery, 
made  the  same  discovery  five  years  later  but  thought  that  the  acid  merely 
combined  with^  the  borax  to  form  the  sedative  salt.  In  1732  Geoffroy 
the  Younger  observed  the  green  color  which  an  alcoholic  solution  of 
this  substance  imparts  to  the  flame  (101).  Although  Louis-Claude 
Bourdelin  thought  this  green  flame  color  must  be  caused  by  the  presence 
of  copper  in  the  sedative  salt,  he  was  unable  to  detect  that  metal  (102). 

In  1747-48  Theodore  Baron  de  Henouville  (1715-1768)  proved 
that  borax  is  composed  of  "sedative  salt"  and  soda  (65).  After  A.  S. 
Marggraf  had  investigated  alumina  ("the  earth  from  alum"),  Baron  de 
Henouville  in  1760  published  a  paper  on  the  basis  of  alum.  Although 
some  of  his  observations  were  erroneous,  he  pointed  out  the  close  rela- 


ELEMENTS  ISOLATED  WITH  K  AND  NA 


575 


tion  between  this  earth  and  "sedative  salt/*  that  is  to  say,  between  the 
compounds  of  aluminum  and  boron  (103). 

In  his  "Elective  Attractions,"  Torbern  Bergman  stated  emphatically 
that  the  so-called  "sedative  salt"  is  not  a  salt  but  an  acid.  "The  substance 
commonly  called  sedative  salt,"  said  he,  "is  more  nearly  allied  to  acids 
than  any  other  class  of  bodies.  It  reddens  turnsole  and  saturates  alkalis 
and  soluble  earths.  It  also  dissolves  various  metals,  and  has  other  prop- 
erties which  shew  its  acid  nature,  and  it  seems  better  entitled  to  the 
name  of  acid  of  borax  than  to  that  of  sedative  salt"  (66). 


Louis-Joseph  Gay-Lussac,  1778-1850. 
Professor  of  chemistry  at  the  ficole  Poly- 
technique  and  at  the  Jar  din  des  Plantes. 
With  Thenard,  he  prepared  potassium 
without  the  use  of  a  battery,  and  iso- 
lated boron.  In  1809  Gay-Lussac  enun- 
ciated his  famous  law  o£  combining  vol- 
umes of  gases. 


After  the  chemical  revolution,  "sedative  salt"  came  to  be  regarded 
as  an  acidic  oxide,  boric  (or  boracic)  acid.  Even  at  the  close  of  the 
eighteenth  century,  its  chemical  nature  was  not  understood.  In  a  letter 
to  the  Annales  de  Chimie  et  de  T^ysique,  A.  N.  Scherer  wrote  in  1799: 
"I  have  just  been  assured  that  Crell  has  recognized  carbon  as  the  radical 
of  boracic  acid"  (67). 

Lavoisier  believed  that  it  contained  oxygen,  and  had  mentioned  its 
radical  in  his  list  of  elements*  (50).  The  first  proof  of  the  composition 
of  boric  acid  was  given  in  1808  when  Gay-Lussac  and  Thenard  in  France 
and  Davy  in  England  succeeded  in  decomposing  it  by  reduction  with 

*  See  Chapter  18,  p.  477. 


576  DISCOVERY  OF  THE  ELEMENTS 

potassium,  and  in  liberating  a  new  element  which  the  French  chemists 
called  bore  and  Sir  Humphry  called  boracium. 

Louis-Joseph  Gay-Lussac  was  bom  at  St.  Leonard,  near  Limoges, 
on  December  6,  1778,  and  was  therefore  just  eleven  days  older  than 
Davy.  After  receiving  his  elementary  education  in  St,  Leonard  he  went 
to  Paris,  and  when  he  was  nineteen  years  old,  he  enrolled  at  the  Ecole 
Polytechnique,  where  he  soon  became  acquainted  with  his  lifelong  friend 
and  collaborator,  Thenard. 

Somewhat  later  he  won  the  friendship  of  C.-L.  Berthollet  at  the 
Ecole  des  Fonts  et  Chaussees,  who  said  to  him,  "Young  man,  your  destiny 
is  to  make  discoveries"  (3),  For  a  time  he  worked  with  Berthollefs  son 
in  a  factory  in  Arcueil  where  chlorine  was  used  to  bleach  linen.  On 
New  Year's  day  in  the  year  1802  Gay-Lussac  became  a  r6p6titeur  at  the 
Ecole  Polytechnique,  where  he  often  substituted  for  Fourcroy  in  his 
lectures  on  chemistry. 

Two  years  later  Gay-Lussac  and  J.-B.  Biot  made  a  daring  balloon 
ascension  to  study  the  behavior  of  a  magnetic  needle  and  the  chemical 
composition  of  the  atmosphere  at  high  altitudes.  On  another  occasion, 
when  Gay-Lussac  alone  had  reached  an  elevation  of  7016  meters  and 
wished  to  ascend  still  higher,  he  threw  overboard  some  small  objects  to 
lighten  the  balloon.  A  shepherdess  in  the  field  was  astonished  to  see 
a  white  wooden  chair  fall  from  the  sky  into  some  bushes,  and  the  peasants 
who  heard  her  story  were  at  a  loss  to  explain  why,  if  the  chair  had  come 
direct  from  Heaven,  the  workmanship  on  it  should  be  so  crude  (3). 

After  a  period  of  extended  travel  and  study  in  Italy  with  Alexander 
von  Humboldt,  Gay-Lussac  returned  to  the  Ecole  Poly  technique  and 
began  a  long  series  of  researches  with  Thenard,  Louis-Jacques 
Thenard,*  a  carpenter's  son,  was  born  at  La  Louptiere  near  Nogent-sur- 
Seine  on  May  4,  1777.  After  receiving  private  instruction  from  the 
village  priest,  he  went  to  Paris  to  study  chemistry,  where,  after  three 
years  of  hard  study  and  severe  privations,  he  finally  succeeded  in 
winning  the  recognition  of  Vauquelin  and  Fourcroy.  The  latter  scientist 
had  befriended  the  poor  peasant  boy  Vauquelin  in  his  early  struggles, 
and  now  Vauquelin  in  turn  helped  Thenard  to  obtain  a  teaching  position 
in  a  Parisian  pension.  In  1798  Gay-Lussac  and  Thenard  met  at  the 
Ecole  Polytechnique,  where  both  later  became  professors. 

When  the  news  of  Davy's  isolation  of  the  alkali  metals  reached 
Paris  in  1808,  Napoleon  provided  Gay-Lussac  and  Thenard  with  a  power- 
ful voltaic  pile.  Before  it  could  be  set  up,  however,  they  showed  that 
these  metals  can  be  obtained  without  a  battery  simply  by  reducing  the 
caustic  alkali  with  metallic  iron  at  a  high  temperature,  a  method  which 

*  He  always  spelled  his  name  thus,  without  the  acute  accent  over  the  e. 


ELEMENTS  ISOLATED  WITH  K  AND  NA  577 


From  Appleton's  "Beginners'  Hand-Sook  of  Chemistry3 


Gay-Lussac  and  Blot  Making  Their  Balloon  Ascension.    Gay-Lussac  was  then 

twenty-five  years  old. 


Davy  soon  adopted  in  preference  to  his  own.  The  potassium  which  the 
French  chemists  prepared  in  this  manner  was  soon  put  to  good  use 
when  they  attempted  to  decompose  boric  acid, 

On  June  21,  1808,  a  note  from  Gay-Lussac  and  Thenard  was  read 
before  the  Institute.  It  announced  that  the  results  they  had  obtained  by 
treating  boric  acid  with  potassium  could  be  explained  only  by  admitting 
that  that  acid  is  composed  of  a  combustible  substance  and  oxygen  (21). 


578  DISCOVEBY  OF  THE  ELEMENTS 

At  the  time  this  notice  was  read,  Gay-Lussac  was  seriously  ill  as  the 
result  of  an  explosion  in  which  he  had  almost  lost  his  sight  (30). 

Before  regarding  their  proof  as  complete,  Gay-Lussac  and  Thenard 
wished  not  only  to  decompose  boric  acid,  but  to  recompose  it  On 
November  30  of  the  same  year  they  were  able  to  state  in  the  Annales 
de  Chimie  et  de  Physique  that  "the  composition  of  boracic  acid  is  no 
longer  problematical  In  fact,"  said  they,  "we  decompose  and  we 
recompose  this  acid  at  will "  Their  method  was  as  follows; 


From  Gay-Lussac  and  Thenard's  "Recherches  Phijsico-Chymiques" 


The  Great  Battery  That  Napoleon  Presented  to  the  Ecole  Polytechnique, 

The  scale  is  25  mm.  for  1  meter.  Figs.  1  and  2  Elevation  and  plan  of  the 
great  battery  Figs.  3  and  4.  Elevation  and  plan  of  two  cells.  a,a,a. 
Barrels'  containing  liquid  for  filling  the  troughs.  b,b,b.  Barrels  containing 
water  for  washmg  the  troughs  c,c,c  Lead  siphons  for  the  flow  of  liquid 
from  the  barrels  d,d,d  Conduits  for  receiving  liquid  from  the  barrels  by 
means  of  the  siphons,  and  conducting  it  into  the  troughs.  e,e,e  Wires  con- 
necting the  different  cells  of  the  battery.  f,f,f  Trough  for  receiving  liquid 
from  all  the  cells  by  means  of  the  individual  troughs,  g,g. 


To  decompose  it,  place  equal  parts  of  metal  [potassium]  and  very  pure, 
vitreous  boracic  acid  in  a  copper  tube  to  which  a  tube  of  bent  glass  is  attached. 
Place  the  copper  tube  in  a  small  furnace,  with  the  end  of  the  glass  tube  in 
a  flask  of  mercury  When  the  apparatus  is  ready,  heat  the  copper  tube 
gradually  until  it  becomes  faintly  red;  keep  it  in  this  condition  for  several 
minutes;  then,  the  operation  being  ended,  allow  it  to  cool  and  take  out  the 
material, 


ELEMENTS  ISOLATED  WITH  K  AND  NA 


579 


Gay-Lussac  and  Thenard  then  gave  a  detailed  description  of  the 
experiment,  saying: 

When  the  temperatuie  is  about  150  degrees,  the  mixture  suddenly  glows 
strongly,  which  appears  m  a  striking  manner  if  a  glass  tube  is  used.  So  much 
heat  is  produced  that  the  glass  tube  melts  slightly  and  sometimes  breaks,  and 
the  air  is  almost  always  driven  out  of  the  vessel  with  force.  From  the 


On  the  First  Page  of  Their 
"Recherches  Physico-Chim- 
iques"  Gay-Lussac  and 
Thenard  thank  Napoleon 
for  the  large  battery  that  he 
had  presented  to  die  Ecole 
Polytechnique. 


RECHERCHES 

PHYSICOCHIMIQUES. 


PREMIERE  PARTIE. 


RECHERCBES 


LA  PILE, 


premier  sola  dab&  ees  redier- 
j  a  d&  etre  de  aous  ocQtrp$r  de  la 

de  la  gyande  b£fcier*e  que 
poly  technique  dolt  i  la  munificence  deS*  M. 
L  et  R,  Cetle  ba^terie  dpnt  jiooss  alloos  c 
ner  In  desorljiticm  ,  est  eo 
paires  carries,  diaqae  paijre 


eoaseqfteut 


beginning  to  the  end  of  the  experiment,  only  atmospheric  air  is  released,  with 
a  few  bubbles  of  hydrogen  gas,  which  do  not  amount  to  the  fiftieth  part  of  that 
given  off  when  the  metal  combines  with  water.  The  metal  [potassium]  is 
used  up  decomposing  part  of  the  boracic  acid;  and  these  two  substances  are 
converted  by  their  mutual  reaction  into  an  olive  gray  material  which  is  a 
mixture  of  potassium,  potassium  borate,  and  the  radical  of  boracic  acid. 
Extract  this  mixture  in  a  tube  by  pouring  water  into  it  and  heating  slowly, 


580  DISCOVERY  OF  THE  ELEMENTS 

and  separate  the  boracic  radical  by  washing  with  cold  or  hot  water      Thai 
which  does  not  dissolve  is  the  radical  itself.   .    .    . 

By  burning  the  new  "radical"  in  oxygen,  or,  better  still,  by  oxidizing 
it  vigorously  with  potassium  chlorate,  potassium  nitrate,  or  nitric  acid, 
Gay-Lussac  and  Thenard  were  able  to  make  some  synthetic  boric  acid, 
a  sample  of  which  they  presented  to  the  Institute.  As  a  result  of  their 
experiments  they  concluded  "that  this  body,  which  we  now  propose  to 
call  bore,  is  of  a  definite  nature,  and  can  be  placed  beside  carbon, 
phosphorus,  and  sulfur;  and  we  are  led  to  think  that  to  pass  into  the 
state  of  boracic  acid  it  requires  a  great  quantity  of  oxygen,  but  that 
before  arriving  at  that  state  it  first  passes  through  that  of  the  oxide" 

(21,  38). 

In  the  following  year  Gay-Lussac  gave  an  even  greater  contribution 
to  chemistry,  his  statement  of  the  famous  law  of  combining  volumes. 
In  later  life  he  taught  chemistry  both  at  the  ficole  Polytechnique  and  at 
the  Jardin  des  Plantes.  After  Bernard  Courtois  discovered  iodine  in  1811, 
Gay-Lussac  and  Thenard  made  a  thorough  study  of  its  properties,  and 
published  their  results  in  a  memoir  now  treasured  by  chemists  as  a  great 
scientific  classic.  Gay-Lussac  died  in  Paris  on  May  9,  1850  (3),  Davy 
once  said  of  him,  "Gay-Lussac  was  quick,  lively,  ingenious,  and  profound, 
with  great  activity  of  mind,  and  great  facility  of  manipulation.  I  should 
place  him  at  the  head  of  all  the  living  chemists  of  France"  (4). 

Besides  carrying  out  many  inorganic  researches  with  Gay-Lussac, 
Thenard  made  important  contributions  to  organic  chemistry.  He  out- 
lived his  famous  collaborator  by  seven  years,  and  when  he  died  on  June 
21,  1857,  at  the  age  of  eighty  years,  his  native  village  honored  him  by 
changing  its  name  to  La  Louptiere-Thenard  (3). 

Davy's  method  of  isolating  boron  was  very  similar  to  that  of  the 
French  chemists.  While  engrossed  in  the  study  of  the  alkalies,  he  had 
passed  a  current  through  boric  acid  and  had  noticed  a  dark,  combustible 
substance  at  the  negative  pole,  but  had  not  at  that  time  thoroughly 
investigated  it  (36) .  In  the  following  year,  however,  he  placed  a  mixture 
of  boric  acid  and  potassium  in  a  copper  tube  and  heated  it  to  dull  redness 
for  fifteen  minutes.  When  he  examined  the  contents,  he  found  that  the 
potassium  had  disappeared  and  that  in  its  place  there  was  an  olive-gray 
powder  which  did  not  effervesce  when  treated  with  water  or  with  acids. 
Davy's  paper  announcing  the  discovery  of  metallic  boron  was  read  before 
the  Royal  Society  on  June  30,  1808  (28,  30). 

In  1909,  Dr.  E.  Weintraub  of  the  General  Electric  Company  ran 
high-potential  alternating  current  arcs  between  cooled  copper  electrodes 
in  a  mixture  of  boron  chloride  with  a  large  excess  of  hydrogen  (51), 
obtaining  pure  fused  boron  which  differed  greatly  in  properties  from  the 
impure  amorphous  product  of  earlier  workers. 


ELEMENTS  ISOLATED  WITH  K  AND  NA  581 

Natural  Boric  Acid  (Sassolite)  In  describing  an  experiment  on  the 
preparation  of  borax  from  sedative  salt  and  natron,  Robert  Dossie  stated 
in  1759.  "Natron  not  being  to  be  obtained  as  a  native  substance,  except 
in  very  few  places,  and  the  sal  sedativus  in  none  hitherto  known,  when 
they  are  required  for  this  experiment,  they  must  be  previously  separated 
from  sea-salt  and  borax"  (104).  Natural  boric  acid  was  first  discovered 
in  a  boiling  hot  spring  in  Tuscany  in  1778  (105).  Hubert  Franz  Hofer, 
a  German  from  Cologne  in  charge  of  the  apothecaries  of  Pietro  Leopoldo, 
Grand  Duke  of  Tuscany,  analyzed  the  water  from  the  hot  springs,  or 
lagoni,  called  Cerchiajo  and  Castelnuovo.  The  Cerchiajo,  or  "hoop" 
spring  at  Monte  Rotondo  had  received  this  name  from  its  property  of 
rendering  wood  soaked  in  it  so  pliable  that  it  could  be  bent  into  a 
hoop.  Hofer  found  that  the  water  contained  from  36  to  72  grains  of 
"sedative  salt"  per  pound,  dependmg  on  the  season  of  the  year  (JOS). 
The  editor  of  the  "Taschen-Buch  fur  Scheidekiinstler  und  Apotheker" 
for  1782  regarded  the  presence  of  "sedative  salt"  in  hot  springs  as  good 
evidence  that  the  borax  from  Holland  and  Venice  must  likewise  be  a 
natural  product  (106). 

Because  of  the  practical  importance  of  Hofer's  discovery,  the 
Academy  of  Sciences  at  Paris  offered  a  prize  for  the  best  paper  (a)  on 
a  chemical  investigation  of  borax  and  sedative  salt  and  the  earth  of 
crude  East  Indian  borax;  (b)  on  the  artificial  preparation  of  borax  or 
sedative  salt  or  on  a  satisfactory  substitute  for  borax,  especially  for 
soldering,  and  (c)  on  the  discovery  of  natural  "sedative  salt'*  (boric 
acid)  elsewhere  than  in  the  marsh  of  Monte  Rotondo  (107). 

In  February,  1779,  Dr.  Paolo  Mascagni  (1755-1815),  professor  of 
anatomy  at  Siena  and  Pisa,  discovered  solid  boric  acid  (sassolite)  at 
the  basins,  or  lagoni,  of  Montecerboli  and  Castelnuovo,  and  published 
a  paper  on  it.  In  another  very  thorough  historical  paper,  published 
twenty  years  later,  he  explained  that  the  term  lagone  is  not  an  augmenta- 
tive of  lago,  a  lake,  but  is  a  corrupted  form  of  the  Latin  lacuna,  a  pond, 
He  described  the  lagoni  as  white,  denuded  areas  with  many  clefts  and 
fissures  "from  whence  one  can  see  rising,  here  and  there,  to  greater  or 
lesser  heights,  varying  amounts  of  white  vapors,  like  clouds  which  dis- 
perse in  the  air  and  vanish,  sending  forth  to  considerable  distances  a 
strong  odor  of  liver  of  sulfur;  and  now  are  seen  various  springs  of  hot 
mineral  water,  which  in  some  places  emerge  quietly  and  are  limpid,  and 
in  others  are  more  or  less  turbid  because  of  continual  agitation  by  the 
vapors  and  exhalations  released  through  the  vents  at  the  bottom  with 
different  amounts  of  force  ...  and  which  produce  more  or  less  boiling, 
together  with  a  rumbling  sound  of  varying  intensity.  ...  If  the  hgoni 
are  visited  long  after  a  rain,  the  ground  is  seen  to  be  entirely  ^covered 
with  varying  amounts  of  inflorescences  and  saline  masses  .  .  ."  (108), 


582  DISCOVERY  OF  THE  ELEMENTS 

These  masses  contained  boric  acid,  ammonium  borate,  sulfates  of  iron 
and  calcium,  and  (occasionally)  magnesium  sulfate. 

In  shallow  places  where  the  water  had  evaporated,  Mascagni  found 
solid  boric  acid  (sassohte)  covering  the  sediment.  On  examining  the 
mud  with  a  lens,  he  saw  clusters  of  small,  shining  crystals.  He  found 
this  solid  boric  acid  in  the  hot  springs  at  Castelnuovo,  Montecerboli, 
Monte  Rotondo,  Edifizio,  Benifei,  Sasso,  Lusfagnano,  and  Serazzano 
(JOS). 

At  least  twenty  years  passed  before  this  discovery  was  utilized.  In 
1799  Dr.  Mascagni  (who  had  previously  been  too  occupied  with  his 
professional  duties)  published  a  plan  for  the  exploitation  of  the  lagoni 
by  increasing  the  surface  of  the  drier  areas  by  piling  up  the  sediment 
into  mounds  exposed  to  the  vapors,  and  allowing  the  natural  heat  of 
the  springs  to  concentrate  the  boric  acid  by  evaporation.  The  last  stage 
of  the  evaporation  was  to  be  carried  out  in  leaden  kettles.  He  suggested 
that  the  boric  acid  be  shipped  to  the  saltpits  at  Portoferrajo,  where  it 
could  be  converted  into  borax,  with  hydrochloric  acid  as  a  by-product 
(108,  109).  Mascagni  taught  anatomy,  physiology,  and  chemistry  for 
a  time  at  the  Santa  Maria  Nuova  Hospital  in  Florence,  and  was  a  friend 
of  Felice  Fontana  (110,  111). 

In  1818  Francesco  Giacomo  de  Larderel  (1789—1858)  founded  the 
Tuscan  boric  acid  industry,  and  nine  years  later  he  succeeded  in  using 
the  natural  steam  as  a  source  of  heat,  thus  making  an  unprofitable 
industry  one  of  the  most  successful  in  Italy.  P.  Le  Neve  Foster,  Jr. 
wrote  in  1875:  "At  the  present  time  there  are  no  less  than  seven  separate 
establishments  belonging  to  Count  Larderel,  all  situated  within  a  few 
miles  of  the  little  town  of  Castelnuovo.  .  .  .  The  works  at  Larderello 
are  the  most  important  of  all.  ...  This  little  colony,  which  was  founded 
by  the  late  Count,  is  situated  at  a  short  distance  from  the  village  of 
Monte  Cerboli,  on  the  torrent  Possera,  and  shows  what  might  be  done 
in  other  parts  of  Italy  for  improving  the  social  condition  of  the  working 
classes.  There  is  a  neat  square,  *La  Piazza  dell'  Industria/  surrounded  by 
blocks  of  buildings,  which  on  one  side  include  the  offices,  church,  museum 
of  mineralogy,  and  schools,  and  on  the  other,  the  model  lodging-houses 
for  the  workmen,  stores,  workshops  for  various  tradesmen,  such  as  tailors, 
shoemakers,  etc.,  and  a  weaving  establishment  for  giving  employment  to 
the  wives  and  daughters  of  the  workmen"  (112).  The  native  boric  acid  is 
found  in  a  region  of  about  one  hundred  square  miles,  between  Pisa  and 
Siena.  Unlike  geysers,  the  soffioni,  or  vents,  eject  more  steam  than  water 
(113,  114,  115). 

Prince  Piero  Ginori  Conti,  Senator  of  the  Kingdom  of  Italy,  devoted 
his  lif  e  to  the  scientific  and  practical  development  of  a  great  modern  boric 


ELEMENTS  ISOLATED  WITH  K  AND  NA  583 

acid  and  borax  industry.  He  was  born  in  Florence  on  June  3,  1865.  After 
receiving  his  doctorate  in  social  science  at  the  Cesare  Alfieri  Institute, 
he  became  interested  in  the  boric  acid  works  of  his  father-in-law,  Count 
Florestano  de  Larderel,  a  grandson  of  Francesco  de  Larderel.  Count 
Florestano  de  Larderel  was  a  patron  of  music  and  of  Pietro  Mascagni, 
composer  of  Caualleria  Rusticana  (110). 

Had  it  not  been  for  the  many  improvements  and  economies  made 
by  Prince  Ginori  Conti  and  his  sons,  the  Italian  boric  acid  industry  might 
have  been  unable  to  survive  after  the  discovery  of  the  great  borax  de- 
posits in  the  salt  crust  marshes  of  Death  Valley,  California  (130).  To 
obtain  larger  amounts  of  volcanic  steam  for  power  and  for  the  large-scale 
production  of  boric  acid,  borax,  liquid  and  solid  carbon  dioxide,  and 
ammonium  carbonate,  Prince  Ginon  Conti  drilled  wells,  often  at  con- 
siderable risk,  and  solved  many  difficult  engineering  problems  (116). 
Among  the  by-products  of  this  industry  are  helium  and  other  inert  gases. 
He  also  developed  the  manufacture  of  a  borosilicate  optical  glass.  Felice 
Sorges  observed  on  his  visit  to  Larderello  not  merely  a  great  center  of 
industry  but  also  many  manifestations  of  the  kindness  and  liberality  of 
the  Prince  and  his  consort  (117). 

In  1926  Prince  Ginori  Conti  attended  the  International  Union  of 
Pure  and  Applied  Science  at  Washington,  D.  C,  and  gave  an  inspiring 
lecture  on  the  use  of  geothermal  power  in  Tuscany,  which  was  later 
published  in  the  Journal  of  Chemical  Education  (115).  His  death  on 
December  3,  1939,  was  an  irreparable  loss  to  chemical  engineering. 

Boracite.  The  first  stony  mineral  of  which  boric  acid  was  recognized 
to  be  a  constituent  was  one  which  G.  S.  O.  Lasms  described  as  a  "cubic 
quartz"  from  Luneburg,  Hanover  (IIS).  It  is  now  known  as  boracite. 
When  Johann  Friedrich  Westrumb,  an  apothecary  in  Hamelin,  analyzed 
it  in  1788,  he  found  lime,  magnesia,  alumina,  silica,  iron,  and,  to  his 
complete  surprise,  about  60  per  cent  of  "sedative  salt."  At  the  close  of 
his  paper  he  conscientiously  stated,  "I  regret  that  I  cannot  get  enough  of 
the  mineral  in  order  to  experiment  with  several  hundred  grains  and 
carry  out  the  decomposition  very  accurately;  for  I  cannot,  like  many 
assayers,  state  the  proportions  in  very  small  quantities  precisely"  (119). 
The  composition  of  boracite  is  expressed  by  the  formula  6MgO  MgCl2 

8B203  (120). 

Borax  in  California.  The  great  deposits  of  borax  and  other  soluble 
salts  in  San  Bernardino  County,  California,  were  discovered  by  Dennis 
Searle  and  E.  M.  Skillings  on  February  14,  1873.  In  the  following  year 
Arthur  Robottom  of  London  explored  the  borax  regions  of  Nevada  and 
California,  "travelled  with  a  mule  team  over  a  very  rough  country  at  the 
rate  of  from  12  to  14  miles  per  day,  and  arrived  at  length  ...  at  the 


584  DISCOVERY  OF  THE  ELEMENTS 

shanty  kept  by  Jim  Bridger,  some  42  miles  from  the  Slate  Range,  and 
which  is  situated  on  the  mam  road  to  Cerre  Gorda,  a  wild  looking 
spot.  ..."  A  pioneer  prospector  who  had  been  to  Death  Valley  told  him 
of  the  plentiful  supply  of  borax  there  but  stated  that  "no  one  knows  what 
it's  good  for"  After  a  short  stay  at  Jim  Bridgets  shanty,  Mr.  Robottom 
"again  proceeded,  steering  for  the  Foot  Hills,  some  22  miles  from  the 
shanty,  then  onward  through  a  great  canon,  or  divide,  partly  covered 
with  salt,  on  emerging  from  which  I  found  myself  on  the  border  of  the 
most  important  borax  lake  yet  discovered  in  the  world.  I  was  met  by 
John  and  Dennis  Searle,  two  men  belonging  to  the  California  discovery 

army  that  sprang  into  existence  in  the  year  1849 These  men,  masters 

of  almost  eveiy  kind  of  handicraft,"  said  he,  "had  made  their  way  to  this 
great  lake  with  a  view  to  exploration.  Consequently,  though  I  can  claim 
to  be  the  first  Englishman  who  visited  the  borax  lake,  the  honour  of  its 
discovery  does  not  rest  with  me.  I  stayed  some  time  in  the  hut  of  these 
men,  and  together  we  examined  the  ground.  I  very  soon  discovered 
natural  borax  of  the  finest  quality  in  a  pure  state,  and  though  Messrs.  John 
and  Dennis  Searle  had  begun  prior  to  my  arrival  to  develop  the  ground, 
the  first  shipment  was  made  by  me  to  England.  The  borax  I  found  was 
crystallized  borax,  in  the  same  form  as  the  regular  borax  of  commerce, 
and  is  the  only  known  deposit  of  natural  borax  yet  discovered  in  the 
world  In  the  centre  of  the  lake  is  a  bed  of  salt  about  five  miles  long; 
on  the  outside  of  this  salt  is  a  deposit  of  carbonate  of  soda,  and  some 
thousands  of  acres  of  land  covered  with  crude  borax,  from  three  inches 
to  two  feet  thick.  The  crude  borax  is  collected  and  put  into  cowhide 
baskets,  carried  to  a  large  boiling-pan,  and  boiled  for  36  hours;  the  solu- 
tion is  then  run  into  vats,  and  the  crystals  form  on  the  sides  of  the  vats. 
After  drying  it  is  put  into  bags,  about  70  Ibs.  in  each  bag,  and  sent  to 
San  Francisco,  a  distance  of  about  420  miles,  and  conveyed  at  that  time 
by  mule  teams3*  (121], 

The  American  Journal  of  Science  for  1889  contains  a  description  by 
Henry  G.  Hanks  of  the  early  process  of  recovering  the  borax.  "The  plant," 
said  he,,  ".  .  .  consists  of  a  large  steam  flue  boiler,  and  a  multitude  of 
boiling  and  crystallizing  tanks.  .  .  .  Fifty  men  and  thirty-five  animals  are 
employed  in  these  works.  The  product  is  hauled  in  wagons  to  Mojave 
station,  a  distance  of  about  seventy  miles,  over  a  sandy  desert,  so  dry 
and  sterile  that  a  supply  of  water  must  be  hauled  in  other  wagons  for 
the  use  of  men  and  animals.  The  fuel  used  has  been  generally  the  sage- 
brush, which  is  gathered  at  heavy  cost  and  thrown  under  the  boilers  with 
pitchforks,  like  hay  into  a  barn,  but  recently,  California  crude  petroleum 
has  been  substituted"  (122), 

Boric  Acid  in  Sea  Water.  In  1865  J.  G.  Forchhammer  detected  boric 
acid  in  sea  water  (123 ) .  "I  have  long  tried/'  said  he,  "to  find  boracic  acid 


ELEMENTS  ISOLATED  WITH  K  AND  NA  585 

in  sea  water,  but  for  a  long  time  all  my  endeavours  were  vain.  Not- 
withstanding, I  felt  convinced  it  must  be  there,  since  both  boracic  acid 
and  borates  are  not  very  rare,  and  a  great  part  of  its  salts  with  lime  and 
magnesia  are  more  or  less  soluble  in  water.  Thus  I  thought  that  water 
from  the  land  must  have  carried  boracic  acid  into  the  sea,  where  it  still 
must  be  accumulating,  since  we  do  not  know  any  combination  by  which 
it  could  be  separated  again  from  the  water.  An  additional  proof  of 
the  correctness  of  this  idea  I  found  in  the  occurrence  of  stassfurthite 
(mostly  consisting  of  borate  of  magnesia),  together  with  all  other  salts 
that  occur  in  sea  water,  in  the  beds  of  rock  salt  at  Stassfurth  in  Germany" 
(123). 

Forchhammer  evaporated  six  pounds  of  sea  water  from  the  Sound 
near  Copenhagen  and  heated  the  residue  to  white  heat  in  a  perfectly 
clean  platinum  crucible.  After  further  purification  of  the  remaining  hemi- 
prismatic  crystals,  he  treated  them  with  alcohol  and  detected  boron  by 
the  green  color  it  imparted  to  the  alcohol  flame  and  the  brown  color  it 
gave  to  curcuma  paper.  In  1877  L.  Dieulafait  found  boric  acid  to  be 
a  normal  constituent  of  sea  water  (124).  Its  presence  in  many  mineral 
waters  has  also  been  demonstrated. 

Boron  in  Plants  and  Animals.  "When  I  had  convinced  myself/'  said 
Forchhammer,  "that  boracic  acid  occurred  in  sea  water,  it  appeared  to  me 
in  the  highest  degree  probable  that  the  organisms  of  the  sea  would 
collect  it,  and  that  it  might  be  found  in  their  ashes,  I  was  so  fortunate 
as  to  begin  my  experiments  with  a  plant  that  contained  it  in  a  rather 
large  quantity,  viz.  the  Zostera  marina.  .  .  .  Even  Fucus  vesiculosus 
contains  the  same  acid,  but  in  a  much  smaller  quantity"  ( 1-23 ) 

Johan  Georg  Forchhammer  was  a  Danish  geologist  and  chemist.  He 
was  born  at  Husum,  Schleswig,  in  1794,  studied  at  Kiel,  and  started  his 
career  as  a  pharmaceutical  chemist  While  still  in  his  early  twenties,  he 
began  to  collaborate  with  H.  C.  Oersted  and  Jens  Esmark.  In  his  doctor's 
dissertation  in  1820  he  distinguished  between  manganic  and  permanganic 
acids.  He  published  about  two  hundred  papers  on  geological  and 
chemical  subjects,  and  made  many  contributions  to  soil  analysis  and 
hydrography.  His  famous  paper  on  the  composition  of  sea  water  was 
first  published  in  Danish  in  1859.  In  completed  form,  it  appeared  in 
English  in  the  Philosophical  Transactions  in  1865,  the  year  of  his  death 

(125,126). 

In  1887  C.  A.  Crampton  of  the  United  States  Department  of  Agri- 
culture examined  36  samples  of  wine  from  different  parts  of  the  country 
and  found  boric  acid  in  all  but  two  of  them.  Hesitating  to  believe  that 
adulteration  could  be  such  a  universal  practice,  he  analyzed  many  speci- 
mens of  natural  grape  juice  and  found  that  boric  acid  is  a  natural  con- 


586  DISCOVERY  OF  THE  ELEMENTS 

stituent  of  California  grapes.  Other  experimenters  found  it  to  be  almost 
universally  present  in  foreign  grapes  and  wines.  Hence  mere  quali- 
tative detection  of  its  presence  in  a  food  does  not  necessarily  prove  that 
boric  acid  has  been  fraudulently  added  as  a  preservative  (127). 

The  bibliography  on  the  minor  elements  and  their  relation  to  plant 
and  animal  nutrition  by  L.  G.  Willis  of  the  North  Carolina  Experiment 
Station  at  Raleigh  lists  sixty  pages  of  abstracts  of  researches  proving 
that  small  amounts  of  boron  are  essential  for  the  normal  growth  of  many 
food  plants  (128,  163).  Its  presence  in  organic  nature  has  been  thor- 
oughly investigated  by  Professor  Gabriel  Bertrand  and  H.  Agulhon,  who 
found  that  it  is  a  normal  constituent  of  the  animal  organism  and  th.;t 
marine  animals  contain  more  of  it  than  do  the  land  forms  (129). 

SILICON 

Quartz  and  Glass.  Rock  crystal  was  used  in  Egypt  for  the  manu- 
facture of  beads,  small  vases,  and  the  corneas  of  the  eyes  of  statues  even 
in  predynastic  times  (131).  When  the  Book  of  Job  was  written,  glass 
(crystal)  must  have  been  very  costly.  Speaking  of  wisdom,  Job  said, 
"The  gold  and  the  crystal  cannot  equal  it"  ( Job  28, 17 )  The  Phoenicians, 
like  the  Egyptians  before  them,  were  skilled  glassworkers.  The  oldest 
known  glass  vessel  is  in  the  British  Museum.  Since  it  bears  the  name 
Tutmosis  (Thothmes  III),  it  is  believed  to  date  back  to  1500  B.C.  (132). 
From  the  excavation  of  an  Egyptian  glassworks  of  the  year  1370  B.C.  in 
Tel-el-Amarna,  Flinders  Petrie  found  that  the  ancient  Egyptians  made 
their  glass  by  fusing  together  quartz  and  an  alkaline  salt  in  clay  crucibles 
(132).  Pliny  the  Elder  was  familiar  with  quartz  and  its  use  in  glass- 
making,  and  gave  a  good  description  of  rock  crystal 

Although  Sir  Humphry  Davy  felt  certain  that  silica  is  not  an  element, 
he  was  unable  to  decompose  it  with  his  powerful  voltaic  pile,  and  was 
also  unsuccessful  in  his  attempts  to  isolate  silicon  by  passing  potassium 
vapor  over  red-hot  silica.  Gay-Lussac  and  Thenard  observed  that  silicon 
tetrafluoride  and  potassium  react  violently  when  the  metal  is  heated,  and 
that  a  reddish  brown,  combustible  solid  is  obtained.  This  was  probably 
very  impure  amorphous  silicon  (37,  39). 

Berzelius  heated  a  mixture  of  silica,  iron,  and  carbon  to  a  very  high 
temperature,  and  obtained  iron  silicide.  When  he  decomposed  this  with 
hydrochloric  acid,  silica  was  precipitated,  and  the  amount  of  hydrogen 
evolved  was  in  excess  of  the  iron,  indicating  that  some  other  metal  must 
have  been  present  (9).  Berzelius  finally  showed  in  1824  that  this  other 
seemingly  metallic  substance  was  derived  from  the  silica,  and  succeeded 
in  preparing  the  amorphous  form  of  it  by  two  methods.  In  the  first  of 


ELEMENTS  ISOLATED  WITH  K  AND  NA  5S7 

these  he  heated  potassium  in  an  atmosphere  of  silicon  tetrafluoride  gas,  as 
Gay-Lussac  and  Thenard  had  done,  and  obtained  a  brown  mass.  When 
this  was  thrown  into  water,  hydrogen  was  freely  evolved,  and  the  new  ele- 
ment silicon  was  precipitated  as  a  dark  brown,  insoluble  powder  contain- 
ing potassium  fluosilicate,  which  is  difficultly  soluble.  Although  Davy, 
Thenard,  and  Gay-Lussac  had  all  handled  the  brown  powder  before,  only 
Berzehus  had  the  patience  for  the  prolonged  washing  required  to  remove 
the  fluosihcate  (9,  32). 

In  his  other  method  Berzelius  heated  the  potassium  fluosilicate  with 
excess  potassium.  The  resulting  potassium  silicide  was  easily  decom- 
posed with  water,  the  amorphous  silicon  settling  to  the  bottom. 

Nothing  is  easier  [said  he]  than  to  procure  this  substance;  the  following 
is  the  method  I  have  adopted:  The  double  fluate  of  silica  and  potash,  or 
soda,  heated  nearly  to  redness  to  drive  off  the  Hygrometric  water,  is  put  into  a 
glass  tube,  closed  at  one  end.  Bits  of  potassium  are  added  and  mixed  with 
the  powder  by  fusing  the  metal  and  gently  rapping  the  tube  It  is  then  heated 
by  the  spirit-lamp,  and  before  it  is  red-hot,  a  feeble  detonation  ensues  and 
the  silicium  is  reduced.  The  mass  is  suffered  to  cool,  and  then  treated  with 
water  as  long  as  it  dissolves  anything.  Hydrogen  gas  is  at  first  evolved,  in 
consequence  of  siliciuret  of  potassium  having  been  formed,  which  cannot 
exist  in  water. 

The  washed  substance  [continued  Beizelius]  is  a  hydruret  of  silicium, 
which,  at  a  red  heat,  burns  vividly  in  oxygen  gas,  although  the  silicium  is  not 
thereby  completely  oxidated;  it  is  then  heated  in  a  covered  platina  crucible, 
the  heat  being  slowly  raised  to  redness  The  hydrogen  alone  is  oxidated,  and 
the  silicium  is  now  no  longer  combustible  in  oxygen,  but  chlorine  attacks  it 
readily.  The  small  portion  of  silica  that  is  formed  may  be  dissolved  by 
fluoric  [hydrofluoric]  acid.  If  silicium  has  not  been  exposed  to  a  strong  red 
heat,  the  acid  dissolves  it,  with  a  slow  disengagement  of  hydrogen.  According 
to  my  synthetical  experiments,  silica  contains  0  52  of  its  weight  of  oxygen 

Berzelius'  product  was  impure  amorphous  silicon.  Zirconium  may  be 
obtained  by  an  analogous  process  (32). 

The  first  crystalline  silicon  was  prepared  by  Henri  Sainte-Glaire 
Deville  in  1854  (9,  31).  In  the  course  of  his  researches  on  aluminum,  he 
decomposed  an  impure  sodium  aluminum  chloride  with  the  voltaic  pile, 
and  obtained  a  gray,  brittle,  granular  melt  containing  10.3  per  cent  of 
silicon.  When  he  dissolved  away  the  aluminum,  some  shining  platelets 
remained. 

Sainte-Claire  Deville  explained  his  results  by  saying  that  an  alloy 
often  behaves  like  a  true  solution  of  one  metal  in  another.  "Thus  it 
is,"  said  he,  "that  carbon,  boron,  and  silicon,  dissolving  like  metals  in 
iron  and  in  aluminum,  separate  from  them  in  cooling,  and  can  be 
obtained  in  the  crystalline  state  by  the  use  of  reagents  which  act  on  the 


588  DISCOVERY  OF  THE  ELEMENTS 

aluminum  and  the  iron  without  attacking  the  carbon,  the  boron,  and 
the  silicon.  This  is  the  principle  of  the  method  which  has  served  for 
the  preparation  of  the  last  two  metalloids  in  the  adamantine  state."  In 
spite  of  the  metallic  luster  of  his  crystalline  silicon,  he  realized  that  the 
element  was  not  a  true  metal.  "On  the  contrary;3  said  he,  "I  think  this 
new  form  of  silicon  bears  the  same  relation  to  ordinary  silicon  that 
graphite  does  to  carbon"  (33,  34,  35). 

Silica  in  Plants  and  Animals.  Diatoms  flourishing  in  both  fresh 
and  salt  water  have  for  untold  ages  been  extracting  silica  from  the  water 
to  build  up  their  exquisitely  designed  cell  walls,  which,  as  these  unicel- 
lular algae  die,  are  constantly  sinking  to  the  bottom  and  forming  deep 
deposits  of  diatomaceous  earth  or  kieselguhr.  J.  G.  Wallerius  found  in 
1760  that  the  ash  of  the  straw  from  rye,  barley,  wheat,  and  oats  easily 
fuses  to  form  a  green  glass  (133,  134).  This  early  observation  of  the 
presence  of  silica  in  grains  was  soon  confirmed  by  L.  von  Crell,  P.  C. 
Abildgaard,  J.  F.  Westrumb,  and  others.  Sir  Humphry  Davy  concluded 
from  similar  experiments  that  the  siliceous  parts  of  plants  are  similar 
in  function  to  the  skeletons  of  animals  (133,  135,  136,  137).  Silica  is 
always  present  in  the  ash  of  plants  (138),  and  in  1811  A.-F.  de  Fourcroy 
and  N,-L.  Vauquelin  detected  it  in  human  bones  (139). 

ALUMINUM 

Aluminum  is  the  most  abundant  metal  on  the  earth's  surface  and 
one  of  the  most  useful  ones,  yet  it  remained  unknown  for  many  centuries. 

Alum  (Aluntte).  Although  the  ancient  Greeks  and  Romans  used 
alum  in  medicine  and  as  a  mordant  in  dyeing,  they  did  not  distinguish 
it  clearly  from  other  natural  astringents  such  as  copperas  (ferrous  sulfate) 
(68,  69, 140, 141).  The  question  as  to  whether  or  not  the  ancients  were 
acquainted  with  true  alum  is  debatable.  Johann  Beckmann,  author  of 
the  famous  "History  of  Inventions,"  answers  it  in  the  negative  (140). 
Herbert  Hoover  however  gave  strong  evidence  that  their  alum  was  a 
rather  impure  product  ranging  in  composition  from  alum  to  vitriol,  and 
that  since  they  were  thoroughly  acquainted  with  soda  (niter),  they  may 
possibly  have  been  able  to  manufacture  alum  artificially  (73). 

Early  alum  works  in  Phocis  near  Ionia  and  in  Lesbos  sold  their 
product  to  the  Turks  for  the  manufacture  of  brilliant  Turkey  red  (68, 
69),  The  manufacture  was  also  carried  on  in  Syria,  at  Foya  Nova  near 
Smyrna,  and  at  Constantinople.  In  1254  A  D.,  Friar  William  De  Rubru- 
quis  (Ruysbroek)  wrote  in  his  journal,  "I  found  many  Frankes  at  Iconium 
[Konia],  and  a  certaine  Januensian  Marchant,  called  Nicholas  de  Sancto 
Syrio.  Who  with  a  certaine  companion  of  his  a  Venetian,  called  Boniface 


ELEMENTS  ISOLATED  WITH  K  AND  NA  589 

de  Molendino,  earned  all  the  Allum  out  of  Turkie,  so  that  the  Soldan 
could  not  sell  any,  but  to  those  two,  and  they  made  it  so  deare,  that  what 
was  wont  to  be  sold  for  fifteene  Bizantians,  is  now  sold  for  fifty"  (70). 

In  about  1459  Bartholomew  Perdix  (Bartolomeo  Perdice,  or  Per- 
nice),  a  Genoese  merchant  who  had  been  in  Syria,  found  a  rock  suitable 
for  alum  on  the  island  of  Ischia;  he  has  been  regarded  as  the  first  to 
introduce  this  industry  into  Europe  (68),  Gino  Testi  gave  evidence, 
however,  that  alum  was  manufactured  in  Italy  long  before  this.  He 
quoted  a  passage  from  Diodorus  Siculus  (first  century  B.C.)  which 
shows  that  the  Romans  profitably  exported  alum  from  Lipari  for  use  in 
Phoenician  dyeing.  According  to  Testi,  the  alum  mines  on  the  island  of 
Ischia  have  been  known  since  the  twelfth  century  A.D.,  and  Perdice, 
already  aware  of  then-  richness,  brought  skilled  workmen  from  Genoa 
who  had  learned  the  trade  in  Rocca  ( Orf a )  but  had  fled  from  Asia  be- 
cause of  the  Turkish  conquests  ( 71 ) . 

Before  1454  Giovanni  de  Castro  learned  the  process  at  Constantinople, 
On  returning  to  Italy  after  that  city  had  fallen  into  the  hands  of  the  Turks, 
he  happened  to  find,  in  about  1462,  in  the  barren  hills  near  Tolfa,  some 
holly  plants  like  those  he  had  seen  growing  near  the  alum  mines  in  Syria. 
On  searching,  he  found  some  white  stones  similar  to  the  Syrian  ore  from 
which  alum  was  prepared  (71).  Unemployed  alum  workers,  brought 
from  Genoa,  "thanked  God  for  having  restored  to  them  their  means  of 
subsistence."  For  this  discovery  Pius  II  granted  Giovanni  de  Castro  a 
generous  annuity  and  had  a  statue  erected  in  his  honor  ( 71 ) .  In  the 
alum  works  at  Tolfa,  Genoese  workmen  dissolved  the  calcined  rock  in 
a  large  volume  of  water,  boiled  the  lye  in  leaden  caldrons,  and  allowed 
it  to  evaporate  spontaneously  in  wooden  vats  (69,  72).  The  so-called 
"Roman  alum"  produced  there  was  the  double  basic  potassium  alum, 
which  crystallizes  in  cubes  rather  than  octahedra  (71,  73). 

As  early  as  1554  an  alum  works  was  established  at  Oberkaufungen, 
Hesse-Cassel,  Germany  (142).  At  the  beginning  of  the  seventeenth  cen- 
tury Sir  Thomas  Chaloner  noticed  the  sickly  green  color  of  the  vegetation 
on  his  estate  at  Guisborough,  Yorkshire,  found  alum  there,  and  founded 
an  industry  (143).  In  1702  E.-F.  Geoffroy  described  the  manufacture  of 
alum  at  Civita  Vecchia  and  Solfatara,  Italy,  in  Yorkshire  and  Lancashire, 
England,  and  in  Sweden.  He  stated  that  "the  same  mine  which  affords 
it  does  also,  or  may  at  least,  afford  sulphur,  nitre,  and  vitriol.  Perhaps 
these  different  minerals,"  said  he,  "are  at  the  bottom  only  one  principle, 
disguised  under  these  four  salts,  according  as  it  has  been  mixed  by 
nature  with  certain  substances  or  according  as  it  has  been  managed  by 
men"  (144).  Geoffroy  concluded  from  his  analysis  of  alum  that  it  "con- 
sists of  an  acid  Salt  of  the  Vitriolick  Kind,  and  an  astringent  Earth  like 
Bole,  or  Chalk,  very  closely  united  together"  (143). 


590  DISCOVERY  OF  THE  ELEMENTS 

J.-P.  de  Toumefort,  who  puraeyed  through  the  Levant  in  1700,  said 
that  "the  Island  of  Milo  [Melos,  Greece]  .  .  .  certainly  abounds  with  all 
the  Materials  necessary  to  the  production  of  Alum  and  Sulphur.  As  for 
Nitre,  there's  none  at  all,  whatever  the  Inhabitants  say,  who  confound  it 
with  alum"  (146).  He  had  the  erroneous  idea  that  the  alum  was  a 
chloride  produced  by  "spirit  of  salt." 

In  the  eighteenth  century,  according  to  Caspar  Neumann,  alum  "was 
used  in  large  quantity  In  some  mechanic  businesses,  particularly  by  the 
dyers,  paper  makers,  goldsmiths,  bookbinders,  for  preserving  watery 
liquors  from  corruption,  for  preserving  anatomical  preparations,  and 
in  the  embalming  of  animal  bodies:  It  is  far  more  powerfully  antiseptic 
than  the  Vitriols"  (147}. 

Although  G.  E.  Stahl  and  Caspar  Neumann  both  believed  that  alum 
contained  lime,  J,  H.  Pott  was  unable  to  prepare  it  from  lime  and  vitriolic 
acid,  but  always  obtained  merely  selenite  (calcium  sulfate)  (74).  When 
Stahl  leached  with  water  a  broken  clay  tube  he  had  used  for  distilling 
spirit  of  vitriol  (sulfuric  acid),  he  obtained  crystals  of  alum  (74).  Pott, 
too,  prepared  alum  from  clay  and  sulfuric  acid  (74). 

Antoine  Baume  stated  that  the  purest  alum  came  from  Civita  Vecchia 
near  Rome  and  that  a  good  grade  of  it  was  also  made  at  Solfatara.  He 
based  his  account  on  the  Abbe  J.-A.  Nollet's  description,  read  before 
the  Academic  des  Sciences  in  1750,  of  his  visit  to  the  Solfatara  alum 
works  and  on  the  Abbe  Mazeas's  memoir  on  the  alumte  mines  of  Tolfa, 
Italy,  and  Polinier,  Brittany,  which  was  published  in  volume  five  of  the 
"Savants  etrangers"  (148). 

After  the  Abb<§  Lazaro  Spallanzani  ( 1729-1799 )  found  an  unworked 
deposit  of  native  alum  (alumte)  in  a  grotto  at  Cape  Miseno,  near  Naples, 
M  H.  Klaproth  analyzed  some  specimens  of  it  which  John  Hawkins 
collected  there.  The  Abbe  Scipione  Breislak  described  the  extensive 
alunite  deposits  at  Solfatara  in  1792-93  and  afterward  became  the  director 
of  an  alum  works  there.  In  his  "Travels  in  the  Two  Sicilies  and  Some 
Parts  of  the  Apennines,"  Spallanzani  wrote:  It  is  well  known  that  for  a 
long  time  alum  and  sal  ammoniac  have  been  extracted  from  this  half- 
extinguished  volcano  (Solfatara)."  The  methods  employed  were  as 
follows:  "In  the  process  for  the  alum,  certain  square  places  were  cleared 
out  in  the  plain  of  Solfatara,  in  which  it  effloresced,  and  the  efflorescences 
were  swept  together,  and  from  them.,  by  methods  well  known,  the  salt 
was  collected  purified/'  The  sal  ammoniac  fumes  were  allowed  to  con- 
dense on  pieces  of  tile  near  the  apertures  from  which  that  salt  issued. 

After  stating  that  there  had  been  some  criticism  of  these  inefficient 
methods,  Spallanzani  added,  "But  we  may  now  hope  that  both  these 
manufactures  may  become  ob]ects  of  importance  under  the  direction  of 
the  Abbe  Breislak  and  the  liberal  patronage  of  Baron  Don  Giuseppe  Bren- 


ELEMENTS  ISOLATED  WITH  K  AND  NA  591 

tano,  who  has  taken  this  celebrated  Phlegrean  field  at  a  constant  rent, 
The  Abbe  .  .  .  has  greatly  extended  the  spaces  allotted  .  .  .  and  surrounded 
them  with  small  ditches"  ( 149 ) .  The  ditches  were  to  prevent  rain  water 
from  diluting  the  alum. 

The  United  States  has  great  deposits  of  alumte  in  Utah,  Arizona, 
Colorado,  Calif  omia,  Nevada,  and  Washington.  By  means  of  the  Kalunite 
process,  alumina  can  be  made  from  alunite  at  a  cost  which  permits  of 
competition  with  alumina  from  bauxite  (161). 

In  an  attempt  to  determine  the  composition  of  alum,  A.  S.  Marggraf 
in  1754  added  pure  alkali  to  several  pounds  of  it  and  precipitated  what 
he  called  the  "earth  of  alum"  (Alaunerde).  After  he  had  thoroughly 
washed  and  dried  this  alumina,  he  tried  in  vain  to  regenerate  the  alum 
by  adding  sulfuric  acid. 

Marggraf  then  collected  clays  from  various  places  in  Germany, 
Silesia,  and  Poland,  and  distilled  them  with  sulfuric  acid,  but  obtained  no 
satisfactory  crystals  of  alum.  When  he  added  fixed  alkali  in  the  proper 
amount,  however,  he  obtained  beautiful,  large  crystals  of  it  (74). 

Marggraf  noticed  that,  when  he  dissolved  the  earth  from  alum  in 
nitric  acid,  evaporated  the  solution,  and  calcined  the  residue,  he  merely 
regenerated  the  "earth"  but  obtained  no  "Balduin's  phosphorus"  (calcium 
nitrate).  He  realized,  therefore,  that  the  earth  in  alum  must  be  different 
from  that  in  chalk  or  limestone.  He  also  demonstrated  the  presence  of 
alumina  in  clay  and  in  roofing  slate  (74). 

Andreas  Sigismund  Marggraf  was  born  in  Berlin  on  March  3,  1709, 
studied  chemistry  and  pharmacy  first  under  his  father  and  then  under 
Caspar  Neumann,  took  the  medical  course  at  Halle,  and  received  further 
chemical  and  metallurgical  training  in  Freiberg  from  the  famous  director 
of  mines,  J.  Fr.  Henckel.  He  devoted  fifty  years  of  his  life  to  scientific 
research,  and  was  a  pioneer  in  analytical  chemistry.  He  proved  that 
potash  and  soda  are  different,  that  calamine  contains  a  peculiar  metal, 
zinc,  and  that  alumina,  magnesia,  and  lime  are  three  distinct  earths,  and 
was  one  of  the  first  persons  to  prepare  phosphorus.  In  1747  he  made 
the  important  discovery  that  sucrose  exists  in  plants  endemic  to  Europe, 
especially  in  the  beet  species  Beta  alba  and  Beta  rubra.  Although  the 
sweetness  had  been  noticed  long  before,  Marggraf  actually  recovered  this 
sugar  from  the  juice  by  crystallization  (40,  86,  162).  Marggraf  died  in 
his  native  city  on  August  7,  1782,  at  the  age  of  seventy-three  years.  D. 
Lorenz  Crell  called  him  the  second  father  of  European  analytical  chem- 
istry (10),  and  he  must  also  have  been  a  great  teacher.  One  of  his  most 
famous  pupils  was  Franz  Karl  Achard  (40). 

M.-J.-A.-N.  de  Caritat  Condorcet  once  said  of  Marggraf,  "Perhaps 
no  physicist  ever  so  completely  excluded  every  system  and  hypothesis 
...  if ,  for  example,  he  admits  Stahl's  doctrine  on  phlogiston,  one  would 


592 


DISCOVERY  OF  THE  ELEMENTS 


think,  from  the  reserve  with  which  he  speaks  of  it,  that  he  had  a  presenti- 
ment that  this  doctrine,  then  so  widely  accepted,  would  soon,  at  least,  be 
overthrown.  His  memoirs  confine  themselves  to  the  statements  of  the 
facts  ...  his  results  have  a  precision  which  was  not  known  before 
him..  ."(75). 


Hans    Christian   Oersted,    1777-1851. 

Danish   physicist,    chemist,   physician, 
and    pharmacist.      Discoverer    of   the 
magnetic  action  of  the  electric  current 
The  first  person  to  isolate  the  metal 
aluminum 


From  Oersted's  "The  Soul  in  Nature" 


In  his  eulogy,  Condorcet  said  that  "M.  Marggraf  had  a  kind,  good- 
natured,  happy  temperament,  his  only  distraction  and  his  greatest  pleas- 
ure except  study  was  a  small  circle  of  friends  and  enlightened  men  who 
could  understand  him  and  to  whom  he  could  say  what  he  believed"  (75) . 

The  attempts  of  Berzelius  and  Davy  to  use  the  voltaic  current  for 


ELEMENTS  ISOLATED  WITH  K  AND  NA 


593 


Courtesy  Ralph  E.  Oesper 

Heinrich  Rheinboldt,  1891-1955.  German-Brazilian  chemist. 
Head  of  the  chemistry  department  at  the  University  of  Sao  Paulo. 
Grandson  of  the  great  German  dye  chemist  Heinrich  Caro.  He 
has  investigated  the  mechanism  of  the  Grignard  reaction,  the 
organic  compounds  of  sulfur  and  its  congeners,  and  the  chemo- 
therapy of  leprosy,  and  has  published  a  fine  collection  of  lecture 
experiments  and  many  articles  and  books  on  all  fields  of  the 
history  of  chemistry.  See  also  refs.  (54)  and  (165). 


594  DISCOVERY  OF  THE  ELEMENTS 

isolating  the  metal  present  in  alumina  were  unsuccessful.  Although  most 
chemical  historians  credit  F<  Wohler  with  the  first  isolation  of  aluminum, 
the  claims  of  Oersted  cannot  be  lightly  dismissed  (11,  42). 

Hans  Christian  Oersted  (41)  was  born  on  Langeland  Island  in 
southern  Denmark  in  1777,  the  year  in  which  Lavoisier  overthrew  the 
phlogiston  theory.  His  father  was  a  rather  unsuccessful  apothecary,  who 
had  very  little  money  for  the  education  of  his  children.  Hans  Christian 
learned  arithmetic  alone  out  of  an  old  schoolbook  and  sometimes  received 
a  little  instruction  from  private  tutors.  When  he  was  twelve  years  old 
he  became  his  father's  assistant  in  the  pharmacy,  where  he  soon  learned 
to  enjoy  his  chemical  duties.  As  he  was  very  eager  to  attend  the  Uni- 
versity of  Copenhagen,  he  studied  conscientiously  until,  at  the  age  of 
seventeen  years,  he  had  earned  the  coveted  certificate  (Reifezeugnis) 
entitling  him  to  matriculation.  His  studies  at  Copenhagen  included 
science,  philosophy,  and  medicine,  and  at  the  age  of  twenty-two  years  he 
received  the  degree  of  Doctor  of  Medicine. 

At  this  time  he  began  to  lecture  on  chemistry  and  metaphysics,  and 
took  over  the  management  of  a  pharmacy.  After  Volta's  discovery  be- 
came known,  Oersted  immediately  became  interested  in  physics  and 
electricity.  When  he  visited  the  famous  universities  in  Germany,  the 
scientists  he  met  were  charmed  by  his  active  mind,  his  youthful  en- 
thusiasm, and  his  almost  childlike  appearance  and  bearing.  In  1806  he 
became  a  professor  of  physics  at  the  University  of  Copenhagen.  His 
fame  rests  chiefly  on  his  epoch-making  discovery  of  the  magnetic  action 
of  the  electric  current  and  the  close  relation  between  electricity  and 
magnetism. 

In  1825,  however,  he  studied  the  chemical  action  of  the  voltaic 
current,  and  tried  to  isolate  chemically  the  metal  believed  to  be  present 
in  alumina.  He  first  prepared  liquid  aluminum  chloride  by  passing  a 
current  of  chlorine  gas  over  a  mixture  of  charcoal  and  alumina  heated 
to  redness.  By  allowing  potassium  amalgam  to  react  with  the  alumi- 
num chloride,  he  prepared  an  aluminum  amalgam,  and  by  distilling  off 
the  mercury  out  of  contact  with  the  arr,  he  obtained  a  metal  that  looked 
like  tin  (11). 

Oersted  gave  the  following  description  of  his  method: 

The  compound  of  chlorine  with  the  combustible  element  of  the  clay 
(aluminum  chloride)  is  volatile  at  a  temperature  which  is  not  much  above 
that  of  boiling  water,  it  is  somewhat  yellowish,  perhaps  however  from  admixed 
carbon;  it  is  soft,  but  still  has  crystalline  form,  it  absorbs  water  with  avidity 
and  dissolves  therein  with  great  ease  and  with  evolution  of  heat.  Rapidly 
heated  with  potassium  amalgam,  it  is  decomposed,  potassium  chloride  and 
aluminum  amalgam  being  formed.  This  amalgam  is  very  quickly  decomposed 
in  contact  with  the  atmosphere  By  distillation  without  contact  with  the 


ELEMENTS  ISOLATED  WITH  K  AND  NA 


595 


atmosphere,  it  forms  a  lump  of  metal  which  in  color  and  luster  somewhat 
lesembles  tin  Moreover  the  author  has  found,  both  in  the  amalgam  and  the 
aluminum,  remarkable  properties  which  do  not  permit  him  to  regard  the  ex- 
periments as  complete,  but  show  promising  prospects  of  important  results 
(42,43). 

Oersted's  product  must  have  been  impure,  metallic  aluminum  con- 
taining mercury,  but  when  Wohler  repeated  the  experiment  he  found  that 
the  gray  molten  mass  formed  by  the  action  of  the  potassium  amalgam 
on  the  aluminum  chloride  volatilized  completely  when  heated  (12,  46). 
Kirstine  Meyer's  careful  study  of  Oersted's  unpublished  notes  and  I. 
Fogh's  and  M.  Tosterud  and  J.  D.  Edwards'  repetitions  of  his  experiment 
show  that  the  great  Danish  physicist  allowed  a  dilute  amalgam  containing 
about  1.5  per  cent  of  potassium  to  react  with  excess  aluminum  chloride, 
and  that  it  is  possible  to  prepare  the  metal  in  this  manner  (42,  44,  45,  53). 

Since  Oersted's  results  were  published  in  an  obscure  Danish  journal, 


Friedrich  Wohler,  1800-1882.  German 
chemist  Student  of  Leopold  Gmelm  and 
Berzehus.  He  was  the  first  person  to  syn- 
thesize urea  and  to  describe  the  properties 
o£  metallic  aluminum.  He  isolated  alu- 
minum, beryllium,  and  yttrium  hy  the 
action  of  potassium  on  the  respective 
chlondes. 


From  Musprati's  "Chemistry,  Theoretical, 
Practical*  and  Analytical" 


they  made  little  impression  on  the  scientific  world*  Nevertheless,  his 
discovery  of  electromagnetism  brought  him  the  prizes,  honors,  and  in- 
fluence he  so  richly  deserved.  He  lived  to  be  seventy-four  years  old  (41 ) . 
Friedrich  Wohler,  one  of  the  most  versatile  chemists  Germany  ever 
produced,  was  born  in  the  little  village  of  Eschersheim  near  Frankfort-on- 
the  Main  on  July  31,  1800.  His  father,  who  himself  had  a  keen  apprecia- 


596 


DISCOVERY  OF  THE  ELEMENTS 


tion  of  Nature  and  a  liking  for  experimentation,  delighted  to  see  the 
same  tastes  and  talents  develop  in  the  young  child  At  the  age  of  fourteen 
years  Wohler  entered  the  gymnasium  at  Frankfort,  where  he  was  regarded 
as  an  average  student  As  he  was  passionately  absorbed  in  collecting 
minerals  and  making  chemical  experiments,  he  frequently  neglected  his 
assigned  lessons,  but  these  hobbies  led  him  to  make  the  acquaintance  of 
some  famous  mineral  collectors,  among  them  Johann  Wolfgang  von 

Goethe  (13). 

Wohler  was  always  greatly  interested  in  new  elements,  Soon  after 
Berzehus  discovered  selenium  in  Swedish  sulfuric  acid,  Wohler  found  that 
the  Bohemian  acid  also  contained  it.  Soon  after  Professor  F.  Stromeyer 
discovered  cadmium,  young  Wohler  sent  him  some  that  he  had  prepared 
from  zinc.  Wohler's  great  ambition  was  to  make  potassium,  but  since 
his  voltaic  pile  made  of  alternate  layers  of  Russian  copper  coins  and  zinc 


This  Wohler  Plaque,  cast  in  aluminum, 
was  presented  to  Dr.  F  B.  Dains  by  Dr 
Howard  M  Elsey,  Westinghouse  Re- 
search Laboratory,  East  Pittsburgh, 
Pennsylvania.  For  the  history  of  it, 
see  ref.  (50). 


plates  was  not  powerful  enough  for  this,  he  devised  a  purely  chemical 
method,  somewhat  similar  to  that  of  Gay-Lussac  and  Thenard,  in  which 
he  heated  a  mixture  of  potash  and  charcoal  to  white  heat  in  a  graphite 
crucible.  Since  his  sister  shared  the  exhausting  labor  of  blowing  the 
bellows,  she  rejoiced  as  much  as  he  did  when  the  shining  globules  of 
metallic  potassium  appeared  (IS). 

The  youthful  Wohler  also  had  many  other  interests.  He  won  prizes 
in  mathematics,  made  oil  paintings  and  etchings,  collected  coins  and  other 
small  objects  from  Roman  ruins,  and  read  with  enjoyment  the  best  German 
poetry.  At  the  age  of  nineteen  years  he  began  his  medical  course  at  the 
University  of  Marburg,  but  in  the  following  year  he  transferred  to  Heidel- 
berg in  order  to  study  under  Leopold  Gmelin  (47).  He  was  deeply  inter- 
ested in  medicine,  and  intended  to  become  a  practicing  physician  special- 


ELEMENTS  ISOLATED  WITH  K  AND  NA 


597 


izing  in  obstetrics.     On  September  2,  1823,  he  received  the  degree  of 
Doctor  of  Medicine,  Surgery,  and  Obstetrics,  insigni  cum  laude  (13). 

He  had  continued  his  chemical  experiments  all  through  his  medical 
course,  and  Professor  Gmelin,  who  had  not  failed  to  notice  his  surprising 
skill,  advised  him  to  relinquish  medicine  for  chemistry.  Wohler  there- 
fore wrote  to  Berzelius  for  permission  to  enter  his  laboratory  in  Stockholm. 
On  August  1  the  great  Swedish  master  gave  his  famous  reply:  "One  who 
has  studied  under  the  direction  of  Herr  Leopold  Gmelin  will  certainly 
find  little  to  learn  with  me.  .  .  .  You  may  come  when  you  wish/' 


Leopold  Gmelin,  1788-1853.  Professor 
of  chemistry  and  medicine  at  Heidel- 
berg. First  author  of  the  "Handbuch 
der  anorgamschen  Chemie."  Discoverer 
of  potassium  fenicyamde  Son  of 
Johann  Friedrich  Gmelin,  the  author  of 
the  "Geschichte  der  Chemie."  Leopold's 
nephew,  Christian  Gottlob  Gmelm,  was 
the  first  to  observe  the  red  color  im- 
parted to  a  flame  by  lithium  salts. 


From  Muspratt's  "Chemistry,  Theoretical, 
Practical,  and  Analytical" 

Berzelius  must  have  realized  at  once  that  he  had  a  remarkable  stu- 
dent, for  he  started  out  by  assigning  Wohler  the  difficult  analysis  of  a 
zeolite.  If  Berzelius  had  a  remarkable  student,  however,  Wohler  also  had 
a  most  unusual  teacher,  for  Berzehus  first  went  through  the  entire  analysis 
himself,  showing  his  student  the  details  of  every  operation.  Whenever 
Wohler  worked  too  hastily,  Berzelius  remarked,  ^Doctor,  that  was  quick, 
but  poor"*  (IS).  Although  Wohler  spent  less  than  a  year  in  Stockholm, 
the  teaching  of  Berzelius  influenced  the  whole  course  of  his  life  and,  like 
his  great  master,  he  made  important  contributions  both  to  organic  and 
to  inorganic  chemistry.  Minds  such  as  these  cannot  be  encompassed 
within  narrow  boundaries.  As  long  as  Berzelius  lived,  he  carried  on  a 
lively  correspondence  with  Wohler,  and  these  letters  are  a  rich  source 
of  pleasure  and  profit  to  all  chemists  interested  in  the  history  of  their 

*  "Doctor,  das  war  schnell,  aber  schlecht" 


598 


DISCOVERY  OF  THE  ELEMENTS 


science.  Wohler  became  a  teacher  of  chemistry  and  mineralogy  at  the 
newly  founded  "Stadtische  Gewerbeschule"  (Municipal  Technical  School) 
in  Berlin  in  1825  and  three  years  later  was  appointed  as  professor  (83). 
It  was  here  that  he  made  the  two  great  discoveries  for  which  his  name 
will  always  be  honored:  the  isolation  of  aluminum  and  the  synthesis  of 

urea. 

As  previously  stated,  Wohler  was  unable  to  obtain  metallic  aluminum 
by  Oersted's  method.  However,  since  the  latter  encouraged  him  to  con- 
tinue his  attempts,  he  prepared  some  anhydrous  aluminum  chloride  by 
Oersted's  method,  and  devised  a  new  plan  for  isolating  the  metal.  After 
adding  an  excess  of  hot  potassium  carbonate  solution  to  a  boiling  hot 
solution  of  alum,  he  washed  and  dried  the  precipitated  aluminum  hy- 


Wohler's  Residence  at  Gottingen 


droxide,  and  mixed  it  with  powdered  charcoal,  sugar,  and  oil  to  form 
a  thick  paste.  Upon  heating  this  paste  in  a  closed  crucible,  he  secured 
a  very  intimate  mixture  of  alumina  and  charcoal,  and  upon  passing  a 
current  of  dry  chlorine  gas  over  this  red-hot  black  mixture,  he  obtained 
anhydrous  aluminum  chloride  (12,  46). 

Wohler  once  said  that  the  method  by  which  he  isolated  aluminum 
in  1827  was  based  on  the  decomposition  of  anhydrous  aluminum  chloride 
by  potassium  and  on  the  stability  of  aluminum  in  presence  of  water. 
Since  the  reaction  is  too  violent  to  be  carried  out  in  glass,  he  used  a 
platinum  crucible  with  the  cover  wired  on.  Although  only  gentle  heat 
was  applied  to  start  the  reaction,  the  crucible  soon  became  white  hot.  It 


Justus  von  Liebig,  1803-1S73.  German  organic  and  agricultural  chemist. 
Professor  of  chemistry  at  Giessen.  Friend  and  collaborator  of  Wohler.  Dis- 
coverer of  the  isomerism  of  silver  fulminate  and  silver  cyanate.  Editor  of 
the  Annalen.  He  devised  a  new  combustion  train  for  determining  the  ulti- 
mate constituents  of  organic  compounds  and  proved  that  animal  heat  and 
energy  are  produced  by  the  combustion  of  food  in  the  body.  See  also  ref.  (79). 


600  DISCOVERY  OF  THE  ELEMENTS 

was  not  badly  attacked,  but  in  oider  to  prepare  aluminum  free  from 
platinum  he  repeated  the  experiment,  using  porcelain  and  Hessian 
crucibles.  When  he  cooled  the  crucible  completely  and  plunged  it  into 
water,  metallic  aluminum  always  separated  as  a  gray  powder.  Wohler 
obtained  only  a  small  quantity  of  the  metal,  and  it  was  not  pure,  but 
contaminated  with  potassium,  platinum,  or  aluminum  chloride  (12}. 
However,  he  was  the  first  to  describe  the  properties  of  aluminum,  and  in 
1845  he  finally  succeeded  in  melting  the  powder  to  a  coherent  metallic 
mass  (49,  54).  He  also  piepaied  beryllium  and  yttrium  in  the  same 
manner  (8). 

Wohler's  life  was  a  long  and  eventful  one.  In  spite  of  his  unceasing 
labors  for  science,  he  found  time  for  many  social  contacts,  and  had  a 
deep  capacity  for  friendship.  The  lifelong  intimacy  between  Wohler  and 
Liebig  caused  the  latter  to  write  in  one  of  his  last  letters : 

Even  after  we  are  dead  and  oui  bodies  long  returned  to  dust,  the  ties 
which  united  us  in  life  will  keep  our  memory  green,  as  an  instance— not  very 
frequent— of  two  men  who  wrought  and  strove  in  the  same  field  without  envy 
or  ill  feeling,  and  who  continued  in  the  closest  friendship  throughout  (14). 

In  1835  Wohler  became  Friedrich  Stromeyer's  successor  as  professor 
of  chemistry  at  Gbttingen,  where  he  taught  for  the  rest  of  his  life.  Wohler 
spent  his  old  age  in  the  midst  of  his  happy  family.  He  had  a  son  and 
four  daughters,  and  when  they  all  visited  their  parents  in  the  summer, 
some  of  them  stayed  with  the  neighbors,  for  the  family  home  was  not 
large  enough  to  hold  all  the  grandchildren.  He  received  high  scientific 
honors  of  all  kinds,  but  none  were  dearer  to  him  than  the  celebrations 
planned  by  his  students  on  the  occasions  of  his  sixtieth,  seventieth,  and 
eightieth  birthdays,  and  on  the  fiftieth  anniversary  of  the  synthesis  of  urea 
(13,  48). 

Some  of  the  most  eminent  chemists  in  the  United  States,  including 
several  who  later  became  presidents  of  the  American  Chemical  Society, 
studied  under  Wohler  (84).  Dr.  Edgar  Fahs  Smith,  America's  great 
chemical  historian,  once  gave  the  following  picture  of  the  aged  Wohler: 

Two  or  three  days  before  Christmas  the  chemical  laboratories  in  the 
University  of  Gottingen  were  nearly  deserted.  Only  a  few  students  remained 
Late  in  the  afternoon,  some  one  began  singing,  "Stille  Nacht,  Heilige  Nacht/' 
One  by  one  the  other  students  in  the  laboratory  gathered  about  the  singer 
and  solemnly  joined  in  the  song.  Soon  we  noticed  that  the  door  of  the 
laboratory  opened  and  in  walked  the  old  Master.  Immediately  he  took  from 
his  head  the  black  skull  cap  he  was  accustomed  to  wear  in  the  laboratories, 
placed  it  under  his  arm,  folded  his  hands,  and  with  bowed  head  stood  just 
inside  the  door  while  the  song  continued  When  the  singing  was  over  the 
old  Master  came  forward  and  said,  "Thank  you,  gentlemen/*  and  withdrew 
.(IS), 


ELEMENTS  ISOLATED  WITH  K  AND  NA 


601 


Photo  loaned  by  Frau  Bucket,  Gottingen,  Germany 

Wohler  in  Later  Life**  Professor  of  chemistry  at  Gottingen.  Famous  for 
his  researches  on  cyanogen,  cyanuric  acid,  and  the  radical  of  benzole  acid, 
and  on  the  metals  titanium,  aluminum,  yttrium,  beryllium,  and  vanadium. 
German  translator  of  Berzelius*  "Textbook  of  Chemistry"  and  Hisinger's 

"Mineral  Geography." 

*  The  author  acknowledges  her  gratitude  to  Drt  L.  C.  Newell  for  the  use  of  this 
portrait. 


602 


DISCOVERY  OF  THE  ELEMENTS 


Wohler  s  room  was  filled  with  portraits  of  his  two  best  friends, 
Liebig  and  Berzelius.  Not  long  before  his  death,  he  hesitatingly  held 
out  to  a  friend  at  parting  a  little  box  wrapped  in  paper,  saying  to  him, 
"Keep  it  in  remembrance  of  me.  Do  not  open  it  until  you  are  on  the 
train,"  The  box  was  found  to  contain  a  spoon  and  the  words,  "A  present 
from  Berzelius,  he  used  this  platinum  spoon  many  years  in  his  researches," 
Wohler  died  on  September  23,  1882.  In  accordance  with  his  wish,  there 
Is  no  bronze  or  marble  monument  to  mark  his  resting  place,  but  only  a 
stone  with  the  name  Friedrich  Wohler  (13). 


Charles  Sainte-Claire  Deville, 
1814-1876.  French  geologist  who 
explored  the  Antilles,  the  Azores, 
and  the  Canary  Islands  and  studied 
the  allotropic  forms  of  sulfur 

Henri  Sainte-Claire  Deville,  1818- 
1881.  Professor  of  chemistry  and 
dean  at  the  University  of  Besangon, 
afterward  professor  of  chemistry  at 
the  Scole  Normale  Supeneure.  He 
discovered  toluene  in  balsam  of 
Tolu,  prepared  anhydrous  nitrogen 
pentoxide,  and  made  sodium  and 
aluminum  on  a  commercial  scale. 


From  Gatfs  "Henri  Sainte-Claire  Deville, 
sa  Vie  et  ses  Travaux" 


The  first  pure  aluminum  was  prepared  by  the  great  French  chemist 
Henri  Sainte-Claire  Deville,  who  was  born  on  the  Island  of  St.  Thomas 
in  the  Antilles  on  March  11,  1818.  Both  Henri  and  his  elder  brother 
Charles  were  educated  at  the  Institution  Sainte-Barbe  in  Paris,  where 
Charles  studied  geology  under  Elie  de  Beaumont  at  the  School  of  Mines, 
while  Henri  took  the  medical  course  and  studied  chemistry  under  Thenard. 
Both  brothers  were  crowned  by  the  Institute,  and  both  were  in  the  same 
section.  Throughout  their  lives  they  had  the  deepest  affection  for  one 


ELEMENTS  ISOLATED  WITH  K  AND  NA 


603 


another,  and  when  one  o£  Henri's  sons  married  Charles's  daughter,  one  of 
the  fathers  remarked,  "My  brother  and  I  do  not  know  how  to  tell  which  of 
the  two  belongs  to  each  of  us,  whether  it  is  my  son  who  has  married  his 
daughter,  or  my  daughter  who  has  married  his  son"  (16). 

Henri's  first  paper,  published  m  1839,  was  a  research  on  turpentine, 
and  two  years  later  he  discovered  toluene  in  balsam  of  Tolu.  His  most 
important  work,  however,  was  m  inorganic  and  physical  chemistry.  In 
1844  conservative  university  officials  were  horrified  to  learn  of  the  appoint- 
ment by  Thenard  of  the  twenty-six-year-old  Henri  Sainte-Claire  Deville 
as  dean  to  reorganize  the  faculty  at  Besan£on.  Nevertheless,  Thenard's 


Louis-L^once  Elie  de  Beaumont,  1798- 

1874.  French  geologist  and  mining  engi- 
neer Perpetual  secretary  of  the  Acad- 
emic des  Sciences.  He  described  the 
course  of  great  nvers  and  the  effects  of 
their  mechanical  work,  and  investigated 
the  materials  ejected  by  volcanoes.  With 
O  -P  -A  Petit-Dufrenoy  he  made  the  first 
accurate  and  complete  geological  map  of 
France, 


mature  judgment  proved  correct,  and  Sainte-Claire  Devilled  career  proved 
to  be  even  more  brilliant  than  he  had  predicted.  While  at  Besangon, 
Sainte-Claire  Deville  devised  new  analytical  methods  for  testing  the 
city  water  supply,  and  succeeded  in  preparing  anhydrous  nitrogen  pent- 
oxide  (17). 

When  A.-J.  Balard,  the  discoverer  of  bromine,  went  to  the  College 
de  France,  Deville  was  called  to  fill  tie  vacancy  at  the  Ecole  Normale 
Sup&ieure,  and  it  was  there  that  the  first  beautiful  aluminum  ingots  were 
made.  Sainte-Claire  Deville  was  attempting  in  18S4  to  prepare  a  proto- 
chloride  of  aluminum  by  allowing  aluminum  to  react  with  the  chloride, 
,  and  in  preparing  his  aluminum  he  used  Wohler's  method,  but 


604  DISCOVERY  OF  THE  ELEMENTS 

substituted  sodium  for  the  potassium  He  noticed  some  large  globules 
of  shining  metallic  aluminum,  and  immediately  set  to  work  to  make  the 
process  commercially  profitable  (35). 

Although  the  first  experiments  weie  made  at  the  Ecole  Normale 
Superieure,  the  generosity  of  Napoleon  III  made  it  possible  for  him  to 
continue  them  on  a  larger  scale  at  the  Javel  works.  Since  Sainte-Claire 


Frank  Fanning  Jewett,  1844-1926.  Re- 
search assistant  at  Harvard  University 
under  Wolcott  Gibbs.  Professor  of 
chemistry  at  the  Imperial  University  of 
Japan  Professor  of  chemistry  and  min- 
eralogy at  Oberlin  College.  His  account 
of  Wohler's  researches  on  aluminum  in- 
spired Charles  M.  Hall  to  search  for  a 
commercial  process  for  preparing  the 
metal. 


Courtesy  H    N    Holmes 


Deville's  commercial  process  required  large  amounts  of  sodium,  it  was 
necessary  for  him  to  perfect  at  the  same  time  a  cheaper  process  for  pre- 
paring that  metal.  When  he  began  his  experiments,  the  price  of  sodium 
was  even  higher  than  that  of  potassium,  but  he  knew  that  sodium  com- 
pounds are  more  abundant  in  Nature  than  those  of  potassium,  and  that 
sodium,  because  of  its  smaller  equivalent  weight,  would  be  the  more 
economical  metal  to  use. 

After  perfecting  a  process  for  the  manufacture  of  sodium  which 
caused  a  rapid  fall  in  its  price,  Deville  attempted  the  large-scale  produc- 
tion of  aluminum.  There  is  found  in  southern  France  and  elsewhere  an 
ore,  bauxite,  named  for  the  village  of  Baux,  near  Aries  in  Provence.  In 
the  Sainte-Claire  Deville  process,  alumina  obtained  from  this  ore  was 
intimately  mixed  with  charcoal,  heated,  and  treated  with  chlorine  to 
form,  the  chloride.  An  excess  of  aluminum  chloride  vapor  was  then  passed 
over  molten  sodium  in  an  iron  tube,  after  which  the  reaction  mass  was 


ELEMENTS  ISOLATED  WITH  K  AND  NA 


605 


transferred  to  iron  or  clay  crucibles  and  heated  to  complete  the  reaction. 
It  was  found  later,  however,  that  the  reaction  proceeds  more  quietly  with 
double  sodium  aluminum  chloride,  which  acts  as  a  flux  and  allows  the 
aluminum  globules  to  coalesce,  and  that  the  fluidity  of  the  charge  can 
be  increased  by  addition  of  cryolite  (IS,  78). 

Certain  trouble  makers  who  were  poor  judges  of  character  tried 
to  create  ill-will  between  Wohler  and  Samte- Claire  Deville,  advising  the 


The  Aluminum  "Crown  Jewels."   In 

this  chest,  carefully  preserved  by  the 
Aluminum  Company  of  America  at 
Pittsburgh,  are  the  original  buttons 
of  the  metal  made  by  Charles  M 
Hall  in  Oberlin,  February  23,  1886 
( left ) ,  the  larger  ones  made  by  Hall 
in  December,  1886  (center),  and  the 
first  button  or  ingot  (right)  produced 
by  the  Aluminum  Company  of 
America 


Courtesy  Ftsher  Scientific  Co 


latter  that,  since  Wohler's  aluminum  was  of  such  doubtful  purity,  he 
ought  to  claim  for  himself  the  honor  of  discovering  the  metal.  The 
French  chemist's  reaction  to  this  counsel  throws  an  interesting  sidelight 
on  his  character.  As  soon  as  he  had  obtained  a  sufficient  quantity  of 
malleable  aluminum,  he  had  a  medal  cast,  bearing  simply  the  name 
Wohler  and  the  date  1827,  and  sent  it  to  the  great  German  master.  Deville 
and  Wohler  always  remained  fast  friends,  and  collaborated  in  a  number 
of  important  researches.  In  his  book  entitled  "L' Aluminium,  ses  Propri- 
et£s,  sa  Fabrication  et  ses  Applications,"  the  former  wrote,  "I  will  say  with 
pleasure  that  I  consider  it  an  unexpected  good  fortune  to  have  been  able 
to  take  a  few  more  steps  in  a  path  opened  by  Berzelius*  eminent  successor 
in  Germany"  (IS). 

In  1854  R.  W.  Bunsen  in  Heidelberg  and  H.  Sainte-Claire  Deville  in 
Paris,  working  independently  of  each  other,  obtained  metallic  aluminum 
by  electrolysis  of  fused  sodium  aluminum  chloride  (54y  80,  81 ). 


606  DISCOVERY  OF  THE  ELEMENTS 

Henri  Sainte-Claire  Deville  also  made  important  investigations  of 
boron,  silicon,  magnesium,  and  the  metals  of  the  platinum  family.  The 
platinum  researches  were  dangerous,  and  he  often  suffered  severely 
from  poisoning  by  the  vapors  of  osmic  acid.  His  fame,  however,  rests  even 
more  on  his  enunciation  of  the  laws  of  gaseous  dissociation.  Sainte-Claire 
Deville  was  described  as  ardent,  vivacious,  charming,  sympathetic,  gay, 
and  generous.  At  the  Ecole  Normale  he  used  to  eat  at  the  students' 
table,  jesting  familiarly  with  them  but  never  for  a  moment  losing  their 
profound  respect  (19).  His  married  life  was  a  most  happy  one,  and 
his  five  sons  were  a  credit  to  their  parents.  He  died  in  1881,  mourned  by 
his  family  and  by  his  scientific  colleagues  throughout  the  world  (18),  and 
the  funeral  oration  was  delivered  by  Louis  Pasteur. 

The  next  scene  of  the  aluminum  drama  is  laid  in  the  United  States. 
Henri  Sainte-Claire  Deville's  process  had  made  the  metal  a  commercial 
product,  but  it  was  still  expensive.  Charles  Martin  Hall,  a  student  at 
Oberlin  College,  inspired  by  the  accounts  which  Professor  F.  F.  Jewett 
had  given  of  his  studies  under  Wohler,  decided  that  his  supreme  aim 
in  life  would  be  to  devise  a  cheap  method  for  making  aluminum.  In  an 
improvised  laboratory  in  the  woodshed,  and  with  homemade  batteries, 
he  struggled  with  this  problem.  On  February  23, 1886,  this  boy  of  twenty- 
one  years  rushed  into  his  professor's  office  and  held  out  to  him  a  handful 
of  aluminum  buttons,  Since  these  buttons  led  to  a  highly  successful 
electrolytic  process  for  manufacturing  aluminum,  it  is  small  wonder 
that  the  Aluminum  Company  of  America  now  treasures  them  and  refers 
to  them  affectionately  as  the  "crown  jewels  "  A  beautiful  statue  of  the 
youthful  Charles  M.  Hall,  cast  in  aluminum,  may  now  be  seen  at  Oberlin 

College  (11,  55). 

At  about  the  same  time  that  Hall  perfected  his  process,  Dr.  Paul- 
Louis-Toussaint  Heroult,  a  young  French  chemist  of  the  same  age,  made 
the  same  discovery  independently,  Dr,  He"roult  was  born  in  1863  at 
Thury-Harcourt  in  the  department  of  Calvados,*  When  the  war  of  1870 
broke  out,  he  was  sent  to  live  with  his  grandfather  in  London,  and  thus 
he  acquired  a  good  command  of  the  English  language.  Three  years 
later  he  returned  to  France  to  continue  his  education. 

At  the  Institution  Sainte-Barbe  he  learned  of  Sainte-Claire  DeviUVs 
researches  on  aluminum,  and  at  the  age  of  fifteen  years  he  read  the 
latter's  famous  treatise.  Using  the  steam  engine  and  dynamo  of  a  small 
tannery  which  he  had  inherited  in  1885,  Heroult  attempted  to  electrolyze 
various  aluminum  compounds.  In  the  following  year,  when  he  was 
attempting  to  electrolyze  cryolite,  his  iron  cathode  melted.  Since  the 
temperature  was  not  high  enough  to  account  for  this,  H6roult  realized  that 

*  Vauquelin,  the  discoverer  of  cfoomium  and  beryllium,  was  also  a  native  of  Calvados. 


Courtesy  Fisher  Scientific  Co. 

Charles  Martin  Hall,  1863-1914.  American  chemist,  inventor,  metallurgist, 
and  philanthropist  who  developed  a  highly  successful  electrolytic  process  for 
manufacturing  aluminum.  This  cheap  method  of  obtaining  the  metal  from 
its  ores  made  possible  the  present  widespread  use  of  aluminum  for  domestic, 

industrial,  and  transportation  purposes. 


608 


DISCOVERY  OF  THE  ELEMENTS 


an  alloy  had  been  f orniecL  A  few  days  later,  when  he  tried  to  lower  the 
temperature  of  the  electrolytic  bath  by  adding  some  sodium  aluminum 
chloride,  he  noticed  that  the  carbon  anode  was  being  attacked.  He 
concluded  that  he  must  be  dealing  with  an  oxide  of  aluminum,  which 
was  being  reduced  at  the  expense  of  the  anode.  This  was  indeed  the  case, 
for  the  sodium  aluminum  chloride  he  had  bought  had  been  previously 


Paul-Louis-Toussaint  Heroult.*  1863- 
1914.  French  metallurgist,  Independ- 
ent discoverer  of  the  electrolytic  method 
of  preparing  aluminum  now  known  as 
the  Hall-Heroult  process.  He  designed 
electric  furnaces,  and  made  many  im- 
portant contributions  to  the  electro- 
metallurgy of  iron  and  steel 


Courtesy  Hobbs,  Bruce  Publishing  Co 


exposed  to  moist  air  and  converted  into  hydrated  alumina.  The  first 
Heroult  patent  for  this  process  was  announced  shortly  before  the  Hall 
patents  (77). 

M,  Heroult  also  made  many  important  contributions  to  the  electro- 
metallurgy of  iron  and  steel.  He  made  frequent  trips  to  the  United  States, 
and  when  the  Perkin  Medal  was  awarded  to  Charles  M,  Hall  in  1911,  M 
Heroult  crossed  the  ocean  in  order  to  be  present  at  the  ceremony  and 
congratulate  him.  By  this  gracious  act,  he  proved  himself  to  be  a  worthy 
successor  of  his  great,  generous  countryman,  Henri  Sainte-Claire  Deville 
(II,  52).  Dr.  Heroult  and  C.  M.  Hall  both  died  in  1914. 

Cryolite.  In  1795  Heinrich  Christian  Friedrich  Schumacher,  Danish 
scientist  and  court  physician,  published  a  description  of  an  unknown 
white,  sparry  mineral  which  had  been  sent  to  Copenhagen  from  Green- 


*  The  author  is  most  grateful  to  Aluminum,  Hobbs,  Bruce  Publishing  Co.,  for  the 
portrait  of  Hefpult 


ELEMENTS  ISOLATED  WITH  K  AND  NA  609 


Frank  Burnett  Dams,  1869-1948.  Lecture  assistant  to  Dr.  W. 
O.  Atwater  at  Wesleyan  University,  Middletown,  Connecticut, 
and  later  assistant  professor  at  Northwestern  University  and 
professor  at  Washburn  College  in  Topelca,  Kansas,  From  1911 
until  the  time  of  his  retirement  in  1942  he  was  in  charge  of  the 
department  of  organic  chemistry  at  the  University  of  Kansas, 
where  he  made  notable  contributions  to  the  chemistry  of  the 
aldehydes,  urea  ethers,  substituted  ureas,  thiazoles,  imidazoles, 
and  pyrazoles,  and  was  an  enthusiastic  collector  of  books,  por- 
traits, and  other  memorabilia  connected  with  the  history  of 
chemistry.  He  was  a  charter  member  of  the  Chicago  Section 
of  the  American  Chemical  Society  and  served  as  Councilor  of 
the  Society,  as  Chairman  of  the  Divisions  of  Organic  Chemistry 
and  History  of  Chemistry,  and  as  contributing  editor  and 
abstractor  for  the  Journal  of  Chemical  Education.  See  also 

ref. 


land  (150).  Three  years  later  Professor  Peder  Christian  Abildgaard 
analyzed  it  and  found  it  to  contain  alumina  and  "acid  of  fluorspar" 
(hydrofluoric  acid).  He  stated  that  nothing  like  it  had  yet  been  found 
in  the  mineral  kingdom  and  that  it  melted  before  the  blowpipe  "like  frozen 
brine/'  From  this  property  it  received  the  name  cryolite  (152). 

When  he  heated  the  pulverized  mineral  with  concentrated  sulfuric 
acid,  it  dissolved  with  evolution  of  hydrofluoric  acid.  When  he  evapo- 
rated the  solution  without  adding  any  alkali,  he  obtained  octahedral 
crystals.  Since  sodium  alum  was  not  yet  known  to  exist,  he  concluded 
that  the  cryolite  must  contain  potassium  (150).  When  the  Brazilian 
scientist  J.  B.  de  Andrada  e  Sylva  described  this  mineral  in  1800,  he  too 
stated  that  it  contained  potassium  (151  ).  Haprotr/s  analysis  in  the  same 


610  DISCOVERY  OF  THE  ELEMENTS 

year  showed,  however,  that  the  alkali  metal  in  the  cryolite  was  not  po- 
tassium but  sodium  (150). 

The  locality  from  which  the  cryolite  had  been  obtained  remained  un- 
known until  1822,  when  Karl  Ludwig  Giesecke,  mineral  dealer  and 
author  of  the  libretto  for  the  Magic  Flute,  found  that  it  came  from  Ivigtut 
on  the  Arsuk  Fjord  in  South  Greenland  and  that  the  deposit  was  much 
more  extensive  than  had  been  believed.  In  the  middle  of  the  nineteenth 
century  Julius  Thomsen  developed  a  great  cryolite  industry  for  the  pro- 
duction of  soda,  aluminum  sulfate,  and  alumina  (150).  In  1866  nearly 
20,000  tons  of  cryolite  were  shipped  from  Greenland.  The  Greenland 
Cryolite  Mining  Company  exhibited  a  mass  of  it,  three  feet  long  by  two 
feet  thick,  from  Ivigtut  at  the  Paris  Exposition  of  1867  (153).  In  1886 
the  Hall-Heroult  process  of  manufacturing  aluminum  by  the  electrolysis 
of  alumina  dissolved  in  molten  cryolite  made  this  metal  available  in 
large  quantities. 

Aluminum  in  Plants  and  Animals.  Lorenz  von  Crell  stated  in  1791 
that  the  presence  of  alumina  in  plants  had  been  established  through  the 
researches  of  Ruckert  (154).  In  1811  A.-F.  de  Fourcroy  and  N.-L, 
Vauquelin  found  aluminum  phosphate  to  be  present  in  human  bones  "in 
very  small  quantity,  yet  enough  for  its  presence  to  be  fully  recognized 
and  established"  (139).  Since  aluminum  in  small  amounts  is  widely 
distributed  in  the  plant  kingdom,  all  animals  consume  some  of  it  with 
their  food.  Thus  minute  amounts  of  it  are  often  found  in  animal  tissues 
(155).  The  presence  of  aluminum  in  many  plants  was  verified  by  M. 
Gabriel  Bertrand,  Professor  Louis  Kahlenberg,  E.  Kratzmann,  Mile. 
Georgette  Levy,  and  many  others  (156, 157,  158, 159).  The  color  of  hy- 
drangeas can  be  changed  from  pink  to  blue  by  addition  of  a  dilute  solu- 
tion of  aluminum  sulfate  to  the  soil  in  which  they  are  grown  (156,  160). 


LITERATURE  CITED 

(1)  NORDENSKIOLD,  A.  E.,  "Scheeles  nachgelassene  Brief e  und  Aufzeichnungen," 

Norstedt  &  Sbner,  Stockholm,  1892,  p.  151.    Letter  of  Scheele  to  Gahn,  Dec. 
26,  1774. 

(2)  JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  Vol.  1,  Baudry  et  Cie.,  Paris,  1891.  pp. 

695-703. 

(3)  BTJGGE,  G.,  "Das  Buck  der  grossen  Chemiker,"  Vol.  1,  Verlag  Cherme,  Berlin, 

1929,  pp.  386-404. 

(4)  DAVY,  J.,  "Memoirs  of  the  Life  of  Sir  Humphry  Davy,  Bart ,"  Vol.  1,  Longman. 

Rees,  Orme,  Brown,  Green,  and  Longman,  London,  1836,  p.  469. 

(5)  MEIXOR,  J.  W,,  "Comprehensive  Treatise  on  Inorganic  and  Theoretical  Chem- 

istry," Vol.  4,  Longmans,  Green  and  Co.,  London,  1923,  pp.  204-7.    Article 
on  beryllium. 

(6)  JAGNAUX,  R,,  "Histoire  de  la  Chimie/'  ref  (2),  Vol.  2,  pp.  169-72. 

(7)  BTJSSY,   A.-A.-B ,   "Preparation  du   glucinium,"   /.    chim.   midicale,    4,   453 

(1828);  Dingl  poly.  ].,  29,  466  (1828). 


ELEMENTS  ISOLATED  WITH  K  AND  NA  611 

(3)     WQHLER,  F.,   "Sur  le  Glucinium  et  I'Yttrium,"  Ann.  chim    phys.,   [2],   39, 

77-S4  (1828). 
(9)     JAGNAUX,  R.,  "Histoire  de  la  Chimie/'  ref.  (2),  Vol.  1,  pp   707-10. 

(10)  CRELL,   L.,   "Lebensgeschichte  A    S    Marggraf's,"  Crell's  Ann,,  5,    181-92 

(1786). 

(11 )  HOLMES,  H.  N.,  "The  story  of  aluminum,"  /.  Chem,  Educ.,  7,  233-44  (Feb., 

1930). 

(12)  JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  ref.  (2),  Vol.  2,  pp   158-64, 

(23)  VON  HOFMANN,  A.  W.,  "Zur  Ennnerung  an  Friedrich  Wdhler/'  Ber ,  15,  3127- 
290  (1882). 

(14}  VON  HOFMANN,  A.  W.  and  EMILIE  WOHLER,  "Aus  Justus  Liebig's  und  Fried- 
nch  Wohler 's  Brief wechsel,"  Vol  2,  F  Vieweg  und  Sohn,  Braunschweig, 
1888,  p.  324.  Letter  of  Liebig  to  Wohler,  Dec,  31,  1871. 

(15)  "Some  experiences  of  Dr    Edgar  F.  Smith  as  a  student  under  Wohler,"  J. 

Chem.  Educ.,  5,  1555  (Dec,  1928). 

(16)  GAY,  JULES,  "Henri  Sainte-Claire  Deville,  Sa  Vie  et  ses  Travaux,"  Gauthier- 

Villars  et  Fils,  Pans,  1889,  p.  5. 

(17)  Ibid.,  p.  9. 

(18)  Ibid,  p.  33. 

(19)  VALLERY-RADOT,  R.,  "The  Life  of  Pasteur,"  Doubleday,  Page  and  Co.,  New 

York  City,  1926,  p.  146 

(20)  "OEUVRES  DE  LAVOISIER/*  Vol  1,  Imprimene  Imperiale,  Paris,  1864,  pp.  135-7 

( 21 )  GAY-LUSSAC,  L.-J.  and  L.-J  THENARD,  "Sur  la  decomposition  et  la  recomposi- 

tion  de  Tacide  boracique,"  Ann  chim  phys.,  [1],  68,  169-74  (Nov.  30, 
1808),  Sci.  News  Letter,  19,  171-2  (Mar  14,  1931). 

( 22 )  KJLAPROTH,  M.  H.,  "Analytical  Essays  towards  Promoting  the  Chemical  Knowl- 

edge of  Mineral  Substances,"  Cadell  and  Davies,  London,  1801,  pp.  325-8. 

(23)  VAUQUEUN,  N.-L.,  "Analyse  de  Faigue  marine,  ou  benl;  et  d^couverte  d'une 

terre  nouvelle  dans  cette  pierre,"  Ann.  chim,  phys ,  [1],  26,  155—77  (May 
( 30  Floreal ) ,  1798  ) ;  "Discovering  the  sweet  element.  A  classic  of  science," 
Sci  News  Letter,  18,  346-7  (Nov.  29,  1930),  Nicholsons  /.,  2,  358-63 
(Nov.,  1798);  393-6  (Dec.  1798). 

(24)  STOCK,  A.  E  ,  "Beryllium/*  Trans.  Electrochem.  Soc ,  61,  255-74  (1932). 

(25)  VAUQUEUN,  N.-L,  "Analyse  de  1'Smeraude  du  Perou,"  Ann.  chim.  phys , 

[1],  26?  259-  65  (June  (30  Prairial),  1798). 

(26)  GMELIN,  J.  F,?  "Analyse  du  beril  de  Nertschinsk  en  Siberie,  et  examen  de 

quelques  caracteres  qui  distinguent  la  glucine  qu'il  contient,"  Ann.  chim. 
phys.,  [1],  44,  27-9  (Oct.  (30  Vendemiarre),  1803),  Crell's  Ann.,  35, 
87-102  (Zweytes  Stuck,  1801). 

(27)  MARGHAL^  G.,  "La  decouverte,  la  preparation,  les  propnetes  et  les  applications 

du  glucinium,"  Chimie  et  Industrie,  22,  1084-92  (Dec.,  1929);  23,  30-3 
(Jan.,  1930). 

(28)  DAVY,  H.,  "Electro-chemical  researches  on  the  decomposition  of  the  earths; 

with  observations  on  the  metals  obtained  from  the  alkaline  earths,  and  on  the 
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(29)  LEBEAUS  P.,  "Recherches  sur  le  glucinium  et  ses  composes,"  Ann.  chim.  phys., 

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(30)  BIOT,   J.-B.,   "Melanges  Scientifiques   et  Litt&raires/'  Vol.   3,   Michel  Levy 

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612  DISCOVERY  OF  THE  ELEMENTS 

(31 )  SAIKTE-CLAIRE  DEVILLE,  H.,  "Note  sur  deux  precedes  de  preparation  de Talu- 
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(37)  FRIEND,  J.  N  ,  "A  Textbook  of  Inorganic  Chemistry/'  Vol  5,  Chas  Griffin  and 

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(39)  Ibid.,  Vol  1,  pp.  313-4,  Vol,  2,  pp  54-65 

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(48)  WARREN,  W.  H.,  "Contemporary  reception  of  Wohler's  discovery  of  the  syn- 

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( 53 )  TOSTERUD,  M  and  J.  D  EDWARDS,  "The  'discovery'  of  aluminum/'  Trans.  Am, 

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(54)  RHEINBOLDT,  H.,  "Hundert  Jahre  Aluminium,"  Sitzungsber.  der  Niederrhein. 

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614  DISCOVERY  OF  THE  ELEMENTS 

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(78)  OESPER,  R.  E.  and  PIERRE  LEMAY,  "Henri  Samte-Claire  Deville,  1818-1881, 

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(79)  OESPER,  R,  E  ,  "Justus  von  Liebig.    Student  and  teacher,    ].  Chem.  Educ  ,  4, 

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(81)  DEVILLE,  H.  SAINTE-CLAIBE,  Compt  rend,  39,  325  (Aug.  14,  1854). 

(82 )  RHEINBOLDT,  HEINRICH,  "Balanga  e  pesagens  na  epoca  preclassica  da  quimica, 

Boletim  da  Associacao  dos  Ex-alunos  de  Quimica  da  Faculdade  de  Filosofia, 
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(83)  Ver,  15,  3146-8  (1882).  „ 

(84)  VAN  KLOOSTER,  H  S./Triedrich  WoHer  and  his  American  pupils,    /.  Ch,em> 

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(85)  LINDBOTH,   STEN,  "Urban  Hiarne  och  Laboratonum  Chymicum,     Lychnos, 

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(86)  COONS,  GEORGE  H.,  "The  sugar  beet     Product  of  science,    Set.  Monthly,  68, 

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(87)  LUCAS,  A.,  "Ancient  Egyptian  materials  and  industries,"  2nd  ed.,  Edward 

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(88)  "Emerald  mines,"  Am.  J  Sci.,  (1),  2,  354  (1820). 

(89)  CALEY,  E.  R,  "The  Stockholm  papyrus.     An  English  translation  with  brief 

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(90)  ACOSTA,  FATHER  JOSEPH  DE,  "Natural  and  moral  history  of  the  Indies,"  Vol.  1, 

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(91)  HOWARD,  JOSEPH  W.,  "Emeralds,"  /   Chem,  Educ,  11,  323-7  (June,  1934). 

(92)  "Gmelin's  Handbuch  .   .   „"  Ref,  (77),  Vol.  26,  pp   1-35,  Vol  29,  pp.  1-16. 

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(94)  SHOKL   A.  T.,  "Mineral  Metabolism,"  Reinhold  Publishing  Corporation,  New 

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(9£)     LEWIS,  WruLiAM.,  "The  Chemical  Works  of  Caspar  Neumann,  M.D.,"  W. 
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(96)  MACQXJER,  P.-J.,  "Elements  of  the  Theory  and  Practice  of  Chymistry/'  2nd 

ed.,  Vol.  1,  A.  Millar  and  J  Nourse,  London,  1764,  p  289;  Vol.  2,  p.  285. 

(97)  ENGESTROM,  GUSTAV  VON,  "Versuche  mit  der  Pounxa,"  Crell's  Neueste  Ent- 

deckungen,  1,  85-8  (1781);  K.  Vet  Acad.  HandL,  34,  319  (1772), 

(98)  ZENZEN,  NILS,  "Om  den  s.  k.  Swedenborgsstammen  och  det  Swedenborgska 

marmorbordet,"  Svenska  Linne-Sallskapets  Arsskrift,  14,  98-9  (1931). 

(99)  LEMERY,  L,,  "Versuche  und  Betrachtungen  uber  den  Borax,"  Crell's  Neues 

chem.  Archiv,  3,  124-5  (1785);  Abh.  konigl.  Akad,  Wiss  (Parw),  1727. 
(700)     MACQUER,  P.-J.,  Ref.  (96),  Vol.  1,  pp.  36-7. 

(101)  GEOFFROY  THE  YOUNGER,  "Neue  Erfahrungen  uber  den  Borax,"  Crell's  Neues 

Chem.  Archiv,  3,  217  (1785);  M£m.  de  I'acad.  roy.  des  sciences  (Paris)., 
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(102)  BOURDELIN,,  L.-JC.,  "Zweite  Abhandlung  uber  das  Sedativsalz,"  Crell's  Neues 

chem.  Archiv,  8,  46-54  ( 1791 ) ;  M£m.  de  math,  et  de  physique,  Acad.  Roy. 
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(103)  BARON  DE  HENOUVTIXE,   THEODORE,   "Ueber  die   Grundlage   des   Alauns," 

Crell's  Neues  chem   Archiv,  S,  178-84  (1791);  M6m.  de  physique,  Acad. 
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ELEMENTS  ISOLATED  WITH  K  AND  NA  615 

(104)  DOSSEE,  ROBERT,  "Institutes  of  Experimental  Chemistry,"  Vol.  1,  J    Nourse, 

London,  1759,  pp.  294-5 

(105)  SCHIFF,  UGO,  "II  Museo  di  Storia  Naturale  .    .    .   di  Firenze,"  Archeion,  9, 
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(106 )  "Taschen-Buch  fur  Scheidekunstler  und  Apotheker,"  Hoffmann  Buchhandlung, 

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(107)  HOFER,  H.  F.,  "Nachricht  von  dem  in  Toskana  entdeckten  naturlichen  Seda- 

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(JOS)  MASCAGNI,  PAOLO,  "Sopra  il  sal  sedafavo  d'Hombergio  o  sia  acido  boracico 
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(Rome),  8,  (1),  487-515  (1799). 

(109)  MASCAGNI,  PAOLO,  "Erste  Abhandhing  uber  die  Boraxsaure  und  die  ver- 

schiedenen  boraxsauren  Salze,  die  man  in  den  Lagoni  von  Volterrano  und 
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der  Chemie,  (2),  6,  181-93  (1806). 

(110)  "Enciclopedia  italiana  di  scienze,  lettere,   ed  arti/*  Vol.  20,   Istituto  della 

Enciclopedia  Italiana,  Rome,  1933,  p.  538,  ibid ,  1934,  Vol.  22,  p.  479. 

(111 )  FEDELI,  CARLO,  "Paolo  Mascagm  e  la  Universita  di  Pisa,  1799-1815,"  Arche- 

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(112)  FOSTER,  P<  LE  NEVE,  JR.,  "The  manufacture  of  boracic  acid  in  Tuscany/' 

Am  Chemist,  5,  455-7  (June,  1875), 
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CASS,  W.  G.,  "The  geothermic  resources  of  Italy,"  Ind.  Eng.  Chem.,  News 

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(115)  CONTI,  PRINCE  PIERO  GZNORIS  "The  utilization  of  geothermal  power  in  Tus- 

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(116)  "Obituary  of  Prince  Ginori  Conti,"  Ind.  Eng.  Chem.}  News  Ed,   18,   108 

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(117)  SORGES,  FELICE,  "Le  visite  agli  stabilimenti  e  region!  industrial!/*  La  Chimica 

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(118)  "Vom  Hrn.   Ingemeiir-Lieut.  Lasius  in  Hannover/*  Crell's  Ann.,   8,  333-6 

(1787). 

(119)  WESTRUMB,  J.  F.,  "Neuentdecktes  Sedativsalz  im  Luneburgischen  sogenann- 

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(120)  KOBELL,  FRANZ  VON,  "Geschichte  der  Mineralogie  von  1650-1860,"  Baierische 

Akad.  Wiss.,  Munich,  18645  pp.  424-5. 

( 121 )  ROBOTTOM,  ARTHUR,  "The  history  of  Califorman  borax/*  Chem  News,  54, 

244-6  (Nov.  12,  1886). 

(122)  HANKS,  H.  G.}  "On  the  occurrence  of  hanksite  in  California/'  Am.  /.  Scit>  137, 

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(123)  FORCHHAMMER,  GsORG,  "On  the  composition  of  sea  water  in  the  different 

parts  of  the  ocean/*  Phil  Trans.,  155,  203-62  (1865). 

(124)  DIEULAFATT,  L,  "I/acide  borique  .    .   ./*  Corn-pi,  rend.,  85,  605-7  (Oct   1, 

1877), 

( 125 )  MEISEN,  V ,   "Prominent  Danish  Scientists  through  the   ages/'  Levin   and 

Munksgaard,  Copenhagen,  1932,  pp.  107-9.  Chapter  on  Forchhammer  by 
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(126)  HANSEN,  P.,  "lUustreret  Dansk  Litteratur  Historic "  2nd  ed.,  Vol.  3,  Det 

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(127)  CRAMPTON,  G.  A.,  "Boracic  acid  as  a  plant  constituent,"  Am.  Chem.  J.,  11, 

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(128)  WILLIS,  L.  G,?  "Bibliography  of  References  to  the  Literature  on  the  Minor 

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columns  9-34. 


616  DISCOVERY  OF  THE  ELEMENTS 

(159)  BERTRAND,  G  and  H.  AGTJLHON,  "Sur  la  presence  normale  du  boie  chez  les 
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2027-9  (June  30,  1913),  "Dosage  lapide  de  1'acide  borique  nonnal  ou 
introdmt  dans  les  substances  alimentaires,"  158,  201-4  (Jan.  19,  1914) 

(ISO)  DINGLEY,  W  F.s  "The  borax  mdustiy  m  Southern  California/'  /  Chem  Educ  , 
8,  2113-25  (Nov,  1931). 

( J3J  )     LUCAS,  A  ,  Ref   (87),  pp  209-11,  214,  352. 

(132)  NEUBURGER,  ALBERT,  "The  Technical  Arts  and  Sciences  of  the  Ancients," 

Methuen  and  Co  ,  London,  1930,  pp   152-3 

(133)  "Kieselerde  auch  em  Bestandtheil  der  Vegetabilien,"  Scherer's  Allgemeines 

J  der  Chemie,  3,  74-5  (1799). 

(134)  WALLERIUS,  J    G,  "Untersuchung  von  der  Beschaffenheit  der  Erde  die  man 

aus  Wasser,  Pflanzen,  und  Thieren  bekommt,"  CtelTs  Neues  chem.  Archiu, 
8,  283-6  (1791),  K.  Vet  Acad  Handl ,  22,  36,  141,  188  (1760)^ 

(135)  "Humphry  Davy's  Versuche  uber  den  Kieselgehalt  der  Pflanzen,"  Scherer's 

Allgemeines  J.  der  Chemie,  3,  75-80  ( 1799 ) 

(136)  GUYTON  DE  MORVEAU,  "Sur  la  sihce  dans  Tepiderme  de  quelques  vegetaux," 

Ann.  chim.  phys.,  (1),  31,  279-83  (1799). 

(137)  SCHERER,  A   N.,  "Sur  Texistence  de  la  silice  dans  les  roseaux  et  les  gramens," 

Ann.  chim.  phys.,  (1),  32, 169-70  (1799). 

(135)  THATCHER,  R  W.,  "The  Chemistry  of  Plant  Life,"  McGraw-Hill  Book  Co., 
New  York,  1921,  p.  5 

(139)  FOURCROY,  A-F.  DE,  and  N.-L    VAUQUELIN,  "Experiments  on  human  bones, 

as  a  supplement  to  the  paper  on  the  bones  of  the  ox,"  Nicholson's  J ,  (2), 
30,  256-60  (Dec,,  1811). 

(140)  BECKMANN,  JOHANN,  "A  History  of  Inventions,  Discoveries,  and  Origins,"  4th 

ed  ,  Vol.  1,  Henry  G.  Bonn,  London,  1846,  pp   180-98, 

(141)  BAILEY,  K    C.,  "The  Elder  Phny's  Chapters  on  Chemical  Subjects,"  Vol    2, 

Edward  Arnold  and  Co ,  London,  1932,  pp  103-5,  233-7,  PLINY,  "Histoiia 
naturahs,"  Book  35,  paragraphs  183-7. 

(142)  CREIGHTON,  M  ,  "A  History  of  the  Papacy,"  Vol  3,  Longmans,  Green  and  Co., 

New  York  and  Bombay,  1897,  pp.  314-15. 

(143)  CULLEN,   EDMUND,    "Physical   and   Chemical   Essays    Translated    from    the 

Original  Latin  of  Sir  Torbern  Bergman,"  Vol.  1,  J.  Murray,  Balfour,  Gordon, 
and  Dickson,  London,  1784,  pp  338-43. 

(144)  MARTYN,  J,  and  E.  CHAMBERS,  "The  Philosophical  History  and  Memoirs  of 

the  Royal  Academy  of  Sciences  at  Pans,"  Vol.  1,  John  and  Paul  Knapton 
et  al ,  London,  1742,  pp.  326-8,  E,-F.  GEOFFROY,  Hist.  Roy.  Acad  Sci. 
(Pans),  1702. 

(145)  GEOFFROY,  E,-F.,  "A  Treatise  of  the  Fossil,  Vegetable,  and  Animal  Substances 

That  Are  Made  Use  of  in  Physik,"  W.  Innys,  R  Manby  et  al,  London, 
1736,  pp.  117-8. 

(146)  TOURNEFORT,  J -P.  DE,  "A  Voyage  into  the  Levant,"  Vol    1,  D    Midwinter, 

R.  Ware,  G.  Rivmgton  et  al ,  London,  1741,  pp.  168,  175-9. 

(147)  LEWIS,  WILLIAM,  Ref.  (95),  p.  189. 

(148)  BAXJME,  ANTOINE,  "Chymie  experimental  et  raisonnee,"  Vol.  3,  P.  F.  Didot 

le  jeune,  Pans,  17733  pp.  462-73. 

(149)  PINKERTON,  JOHN,  "A  General  Collection  of  the  Best  and  Most  Interesting 

Voyages  and  Travels  in  All  Parts  of  the  World,"  Vol.  5,  Longman,  Hurst, 
Rees,  and  Orme,  London,  1809,  pp.  32  and  45.  Spallanzanfs  "Travels  in 
the  two  Sicilies  " 

(150)  DIERGART,  PAUL,  "Beitrage  aus  der  Geschichte  der  Chemie  dem  Gedachtms 

von  G.  W.  A.  Kahlbaum/'  Franz  Deufacke,  Leipzig  and  Vienna,  1909,  pp. 
500-08.  Chapter  by  S.  M.  Jorgensen,  "Zur  Geschichte  des  Kryohths  und 
der  Kryolith-Industrie." 


ELEMENTS  ISOLATED  WITH  K  AND  NA  617 

(151)  ANDRADA,  J.   B.   DE,   "Kurze   Angabe   der   Eigenschaften  und   Kennzeichen 

emiger  neuen  Fossilien  aus  Schweden  und  Norwegen  .   .   .  >"  Scherer's  Allg 
J.  der  Chemie,  4,  28-39  (Jan ,  1800). 

(152)  Scherer's  J ,  2,  502  ( 1798 ) , 

(153)  BLAKE.,  W  P.,  "Notes  upon  some  of  the  mineralogical  curiosities  of  the  Pans 

Exposition  of  1867,"  Am  J.  Sci ,  (2),  45,  197  (March,  1868). 

(154)  WALLERIUS,  J.  G  ,  Ref.  (134),  Footnote  to  p   285 

(155)  SHOHL,  A.  T,  Ref.  (94),  pp   235-6 

(156)  WILLIS,  L  G  ,  Ref   ( 128),  3rd  ed  ,  columns  1-13 

(157)  BERTRAND,  G    and  G,  LEVY,  "The  content  o£  plants,  notably  food  plants,  in 

aluminum,"  Compt  rend,  192,525-9  (1931), 

(158)  KAHLENBERG,  L.  and  J    O.  GLOSS,  "On  the  presence  of  aluminum  in  plant 

and  animal  matter,"  ]  Bwl  Chem  ,  83,  261-4  ( 1929) 

(159)  KRATZMANN,  E.,  "The  microchernical  detection  and  distribution  of  aluminum 

in  the  plant  kingdom,"  Sitzungsber  K.  AkacL  Wiss.  (Vienna),  Math.-Naturw. 
Kl,  122,  311-36  (191-3). 

(160)  CHENERY,  E    M  ,  "The  problem  of  the  blue  hydrangea,"  J   Roy.  Hort.  Soc , 

62,  304-20   (1937),  R,  C    ALLEN,  Proc.  Am.  Soc.  Hort    Sci ,  32,  632-4 
(1934). 

(161)  ANON.,  "New  process  purifies  aluminum  from  alunite,"  Science  News  Letter, 

40,  3  (July  5,  1941). 

(165)     BROWNE,  C.  A.,  "A  source  book  of  agricultural  chemistry,"  Chronica  Botamca, 
1944,  pp  116-17. 

(163)  WOODBRIDGE,  C    G.,  "The  role  of  boron  in  the  agricultural  regions  of  the 

Pacific  Northwest,"  Sci.  Mo.,  70,  97-104  (Feb.,  1950). 

(164)  ADAMS,  F.  D.,  "The  Birth  and  Development  of  the  Geological  Sciences," 

Dover  Publications,  Inc.,  New  York,  1954,  pp.  205-7. 

(165)  OESPER,  R  E  ,  ''Hemrich  Rheinboldt,"  J.  Chem.  Educ.,  27,  296  (June,  1950). 

(166)  WEEKS,  M.  E.,  "Frank  Burnett  Dams/'  Ind.  Eng.  Chem.,  News  Ed.,  13,  118 

(March  20,  1935),  ANON.,  Chem  Eng.  News,  26,  264  (Jan.  26,  1948). 


From  Muspratt's  "Chemistry  Theoretical, 
Practical,  and  Analytical** 

Robert  Wilhelm  Bunsen,  1811-1899.  German  chemist  who  investigated 
the  cacodyl  radical,  the  geysers  of  Iceland,  and  the  chemical  action  of 
light.  Inventor  of  the  Bunsen  battery,  the  grease-spot  photometer,  ice 
and  vapor  calorimeters,  the  thermoregulator,  the  constant-level  water- 
bath,  and  the  filter  pump. 


Nur  immer  zul  wir  wollen  es  ergriinden, 

In  deinem  Nichts  hoff'  ich  das  All  zu  finden  (1). 

But  go  on!    We  want  to  fathom  it. 

In  thy  nothing  I  hope  to  find  the  universe. 

Thus  there  was  for  him  nothing  small  or  great  in 
Nature.  Every  phenomenon  embraced  for  him  an 
endless  diversity  of  factors,  and  in  the  yellow  -flame 
of  an  ordinary  alcohol  lamp  whose  wick  was 
sprinkled  with  salt,  he  saw  the  possibility  of  accomp- 
lishing the  chemical  analysis  of  the  most  distant  stars 
(2). 

So  gab  es  fur  ihn  nichts  Kleines  oder  Grosses  in  der 
Natur.  Jede  Erscheinung  umfasste  ihm  eine  un- 
begrenzte  Mannigfaltigkeit  von  Faktoren,  und  in  der 
gelben  Flammc  einer  gewohnlichen  Weingeistlampe, 
deren  Docht  mit  Salz  bestreut  war,  sah  er  die 
Moglichkeit,  die  chemische  Analyse  der  fernsten 
Gestirne  auszufuhren. 


23 

Some  spectroscopic  discoveries 


Many  elements  are  present  in  the  earth's  crust  in  such  minute 
amounts  that  they  could  never  have  been  discovered  by  ordinary 
methods  of  mineral  analysis.  In  1859,  however,  Kirchhoff  and 
Bunsen  invented  the  spectroscope,  an  optical  instrument  consist- 
ing of  a  collimator,  or  metal  tube  fitted  at  one  end  with  a  lens 
and  closed  at  the  other  except  for  a  slit,  at  the  focus  of  the  lens., 
to  admit  light  -from  the  incandescent  substance  to  be  examined, 
a  turntable  containing  a  pnsm  mounted  to  receive  and  separate 
the  parallel  rays  -from  the  lens;  and  a  telescope  to  observe  the 
spectrum  produced  by  the  prism.  With  this  instrument  they 
soon  discovered  two  new  metals,  cesium  and  rubidium.,  which 
they  classified  with  sodium  and  potassium,  which,  had  been 
previously  discovered  by  Davy,  and  lithium.,  which  was  added 
to  the  Ust  of  elements  by  Arfwedson.  The  spectroscopic  dis- 
covery of  thallium  by  Sir  William  Crookes  and  its  prompt 
confirmation  by  C.-A.  Lamy  soon  followed.  In  1863  F.  Reich 
and  H.  T.  Richter  of  the  Freiberg  School  of  Mines  discovered 
a  very  rare  element  in  zinc  blende,  and  named  it  indium  because 
of  its  brilliant  line  in  the  indigo  region  of  the  spectrum, 


he  Swiss-German  alchemist  Leonhard  Thurneysser  (1531— 
1596)  recognized  several  substances  by  their  behavior  when  heated  and 
by  the  colors  they  impart  to  the  flame,  and  described  his  method  of  analysis 
in  a  poem  that  begins: 

"Des  Schlichs  Gehalt  du  im  Gliihen  kennst 
An  der  Farbe  der  Flamme,  wenn  du  ihn  brennst" 
(91,  92) 

What  the  slime  contains,  the  glowing  reveals 
By  the  flames  bright  hue  when  you  ignite  it. 

Sir  Henry  E.  Roscoe  stated  in  his  "Spectrum  Analysis":  "So  long 
ago  as  1752,  Thomas  Melvill  [or  Melville],  while  experimenting  on 
certain  coloured  flames,  observed  the  yellow  soda  flame,  although  he 
was  unacquainted  with  its  cause"  (63.,  64), 

In  1758  A.  S.  Marggraf  noticed  the  yellow  color  imparted  to  a  flame 

619 


From  a  painting  by  Karla  Fischer,  1909. 
Courtesy  Bausch  &  tomb  Optical  Co. 

In  1&I8  Joseph  Fraunhofer  (1787-1826)  exhibited  his  newest  spectroscope 
before  Counselor  Utzschneider  and  Mr.  Reichenbach,  his  partners  in  the 
glassworks  and  optical  establishment  at  Benediktbeuern.  He  discussed  with 
them  his  latest  researches  on  the  diffraction  of  light  which  had  led  him  to  the 
discovery  of  grating  spectra.,  the  exact  measurement  of  wave  lengths,  and  a 
brilliant  confirmation  of  the  undulatory  theory  of  light. 

by  sodium  salts  and  the  lavender  color  imparted  by  potassium  salts  (3). 
In  1802  Dr.  Wollaston  examined  the  spectrum  of  a  candle  flame  through 
a  prism,  and  saw  the  discontinuous  band  spectrum  (4,  22).  He  said 
(33): 

When  a  very  narrow  line  of  the  blue  light  at  the  lower  part  of  the 
flame  is  examined  alone,  in  the  same  manner,  through  a  prism,  the  spectrum, 
instead  of  appearing  a  series  of  lights  of  different  hues  contiguous,  may  be 
seen  divided  into  five  images,  at  a  distance  from  each  other.  The  1st  is 
broad  red,  terminated  by  a  bright  line  of  yellow;  the  2nd  and  3rd  are  both 
green;  the  4th  and  5th  are  blue,  the  last  of  which  appears  to  correspond 
with  the  division  of  blue  and  violet  in  the  solar  spectrum,  .  .  . 

In  1814  Joseph  Fraunhofer,  a  young  German  physicist  who  had  had 
thorough  training  in  the  art  of  glassmaking,  made  an  unusually  fine 
prism,  saw  for  the  first  time  the  dark  lines  in  the  sun's  spectrum,  and 


SOME  SPECTROSCOPIC  DISCOVERIES 


621 


Courtesy  S»  E.  Sh&ppard 

William  Henry  Fox  Talbot,  1800-1877.  English  antiquarian,  physicist, 
and  pioneer  in  optics  and  photography.  One  of  the  first  to  decipher  the 
Assyrian  inscriptions  at  Nineveh.  In  1839  he  made  negative  prints  on  silver 
chloride  paper,  and  two  years  later  he  invented  the  calotype  process  for 

making  positives. 


622 


DISCOVERY  OF  THE  ELEMENTS 


Sir  David  Brewster  1781-1868,  Scottish  physicist 
famous  for  his  researches  on  the  absorption,  reflec- 
tion, refraction,  and  polarization  of  light,  and  on 
doubly  refracting  crystals.  One  of  the  founders  of 
the  British  Association  for  the  Advancement  of  Science. 
He  invented  the  kaleidoscope  and  improved  the  stereo- 
scope. His  optical  researches  led  to  great  improve- 
ment in  the  construction  of  lighthouses. 


designated  eight  of  the  most  prominent  ones  by  letters  (3,  23).  Ten 
years  later  Sir  John  Herschel  showed  that  a  small  amount  of  an  alkali 
can  be  detected  by  its  flame  spectrum,  Later,  however,  the  presence 
of  the  orange-yellow  lines  of  sodium  in  almost  every  source  he  investi- 
gated prevented  him,  as  it  did  many  another  scientist,  from  realizing 
that  each  element  has  its  own  characteristic  spectrum  (53).  Henry 


SOME  SPECTROSCOPIC  DISCOVERIES 


623 


Fox  Talbot  (24),  an  English  scientist,  found  in  1834  that,  with  the  aid 
of  a  prism,  he  could  distinguish  lithium  from  strontium,*  even  though 
the  salts  of  both  give  red  flames  (4,  26,  32).  He  stated  that  the  dark 
lines  previously  observed  by  Sir  David  Brewster  (33)  in  the  spectrum 
of  light  which  had  passed  through  vapors  of  nitrous  acid  were  caused 
by  absorption  of  light  (5,  25). 


Dr.  David  Alter,  1807-1881,  American 
physician,  physicist,  and  inventor.  He 
observed  the  spark  spectra  of  various 
metals  and  gases  and  predicted  that  "the 
prism  may  also  detect  the  elements  in 
shooting  stars,  or  luminous  meteors." 
See  also  ref  (63). 


Courtesy  W    A    Hamor 


In  1854  David  Alter  of  Freeport,  Pennsylvania,  showed  that  each 
element  studied  had  its  own  spectrum  (53,  54,  56).  At  an  early  age 
he  read  books  on  electricity  and  "natural  philosophy"  (physics),  and 
later,  while  he  was  practicing  medicine,  he  found  time  to  design  and 
invent  several  electrical  devices,  to  construct  lenses,  prisms,  telescopes, 
and  spectroscopes,  and  to  make  an  excellent  daguerreotype  of  the  dark 
lines  of  the  solar  spectrum.  From  a  mass  of  brilliant  glass  found  in  the 
pot  of  a  glass  factory  destroyed  in  the  great  Pittsburgh  fire  of  1845  he 
constructed  a  fine  prism  for  his  spectroscope.  In  1854,  in  his  paper 
"On  certain  physical  properties  of  light  produced  by  the  combustion  of 
different  metals  in  the  electric  spark,  refracted  by  a  prism/'  he  pointed 
out  that  an  alloy  of  two  metals  shows  the  lines  of  both,  and  clearly 
stated  that  each  element  has  a  characteristic  spectrum  (53,  54).  He 

*  Strontium  salts  were  very  rare  at  that  time,  and  Talbot  was  indebted  to  Michael 
Faraday  for  the  specimen  he  used. 


624 


DISCOVERY  OF  THE  ELEMENTS 


Bunsen's  Old  Laboratory  at  Heidelberg,  now  torn  down 

was  not  confused  by  the  universal  presence  of  the  sodium  lines.  In 
1855,  in  his  paper  "On  certain  physical  properties  of  the  light  of  the 
electric  spark,  within  certain  gases,  as  seen  through  a  prism/'  Dr.  Alter 
predicted  that  "the  prism  may  also  detect  the  elements  in  shooting  stars, 
or  luminous  meteors"  (53,  54).  A  few  years  later  G.  R.  Kirchhoff  and 
Robert  Bunsen  firmly  established  the  science  of  spectroscopic  analysis. 

Robert  Bunsen  was  the  son  of  a  professor  of  modern  languages  at 
Gottingen,  and  was  born  in  that  city  on  March  31,  1811.  After  attending 
the  academy  at  Holzminden  he  entered  the  University  of  Gottingen, 
and  studied  chemistry  under  Professor  Friedrich  Stromeyer.  At  the 
age  of  twenty  years  he  received  his  degree  of  doctor  of  philosophy. 
This  does  not  mean  that  Bunsen  was  precocious,  for,  as  Wilhelm  Ostwald 
explains,  students  graduated  at  a  much  earlier  age  then  than  they  do 
now. 

Aided  by  a  grant  from  the  Hanoverian  government,  the  youthful 
Bunsen  broadened  his  scientific  education  by  traveling,  mostly  on  foot, 
through  Germany,  France,  Austria,  and  Switzerland,  and  meeting  the 
scientists  of  those  countries.  For  three  years  he  went  about  studying 
geological  formations,  visiting  factories  and  mines,  and  meeting  technical 
men  and  professors  (2).  In  1836  he  succeeded  Friedrich  Wohler  at 
the  higher  technical  school  at  Cassel.  After  serving  in  similar  positions 
at  Marburg  and  at  Breslau,  he  finally  became  Leopold  Gmelm's  suc- 
cessor at  Heidelberg,  where  he  taught  for  thirty-eight  years,  finally 
retiring  at  the  venerable  age  of  seventy-eight  years  (2,50), 

Bunsen's  very  first  paper  contained  a  discovery  of  great  benefit  to 


SOME  SPEtTTROSCOPIC  DISCOVERIES 


625 


humanity,  for  he  showed  that  freshly  precipitated  feme  hydroxide  is  an 
antidote  for  arsenic  poisoning.  His  impoitant  and  dangerous  research 
on  cacodyl  was  carried  out  at  Cassel  and  Marburg,  Since  his  laboratory 
at  Cassel  was  not  equipped  with  hoods,  he  wore  a  mask  with  a  long  tube 
leading  to  the  fresh  air.  While  he  was  investigating  cacodyl  cyanide, 
an  explosion  occurred  which  shattered  the  mask,  destroyed  the  sight 
of  his  right  eye,  and  nearly  ended  his  life,  yet,  after  he  recovered  from 
the  resulting  critical  illness,  he  carried  the  research  to  a  successful  con- 
clusion. 


Heinrich  Debus,  1824-1915.  German 
chemist  who  taught  for  many  years  at 
Guy's  Hospital,  London,  and  at  the  Royal 
Naval  College,  Greenwich  He  prepared 
pure  purpunn,  discovered  glyoxylic  acid, 
glyoxal,  and  glyoxaline,  and  reduced 
hydrocyanic  acid  to  methylamme  He 
wrote  a  delightful  biography  of  his  pro- 
fessor, Robert  Bunsen. 


This  serious  accident  made  him  very  cautious.  When  one  of  his 
students,  Heinrich  Debus,  once  wished  to  use  some  mercuric  fulminate 
in  a  research,  Bunsen  objected  and  said  (6), 

When  I  came  to  Marburg,  I  found  in  the  collection  of  preparations  a 
glass-stoppered  bottle  containing  an  ounce  or  more  of  mercuric  fulminate. 
I  took  the  flask  and  carried  it  to  a  nearby  deep  stone-quarry,  and  threw  it  in. 

Bunsen  made  a  thorough  study  of  the  gases  of  the  blast  furnace, 
and  it  was  in  this  connection  that  he  developed  his  famous  methods 
of  gas  analysis.  He  invented  the  carbon-zinc  battery,  the  grease-spot 
photometer,  and  the  ice  and  vapor  calorimeters,  and  perfected  the 
Bunsen  burner  (61).  After  the  famous  eruption  of  Mount  Hekla  in 
1845,  he  went  with  a  Danish  expedition  to  study  the  active  hot  springs 
and  geysers  of  Iceland,  and  by  careful  thermometric  measurements,  made 
at  great  risk,  explained  their  action  before  any  scientific  description  of 
the  American  geysers  had  been  given  (7y  27,  57). 


626  DISCOVERY  OF  THE  ELEMENTS 

CESIUM 

Bunsen  afterward  carried  out  an  elaborate  series  of  photochemical 
researches  with  his  lifelong  friend,  Sir  Henry  Roscoe,  but  suddenly 
discontinued  this  work.  The  reason  for  this  may  best  be  told  in  his 
own  words  as  quoted  from  his  letter  to  Roscoe  written  on  November 
15,  1859  (7): 

At  present  [said  he]  KirchhofF  and  I  are  engaged  in  a  common  work 
which  doesn't  let  us  sleep.  ,  .  Kirchhoff  has  made  a  wonderful,  entirely 
unexpected  discovery  in  finding  the  cause  of  the  dark  lines  in  the  solar 
spectrum,  and  increasing  them  artificially  in  the  sun's  spectrum,  and  in  produc- 
ing them  in  spectra  which  do  not  have  lines,  and  in  exactly  the  same  position 
as  the  corresponding  Fraunhofer  lines.  Thus  a  means  has  been  found  to 
determine  the  composition  of  the  sun  and  fixed  stars  with  the  same  accuracy 
as  we  determine  sulfunc  acid,  chlorine,  etc ,  with  our  chemical  reagents.  Sub- 
stances on  the  earth  can  be  determined  by  this  method  just  as  easily  as  on  the 
sun,  so  that,  for  example,  I  have  been  able  to  detect  lithium  in  twenty  grams  of 
sea  water. 

Gustav  Robert  Kirchhoff,  a  young  professor  from  Konigsberg, 
Prussia,  who  had  recently  followed  Bunsen  from  Breslau  to  Heidelberg, 
is  generally  regarded  as  Bunsen's  greatest  discovery  of  the  Breslau 
period.  Kirchhoff  was  born  in  Konigsberg  on  March  12,  1824,  the  third 
son  of  a  counselor  of  justice.  When  he  was  twenty-four  years  old,  he 
became  a  member  of  the  teaching  staff  at  the  University  of  Berlin.  After 
serving  for  a  time  as  professor  extraordinary  at  Breslau,  he  went  to 
Heidelberg  in  1854,  and  collaborated  with  Bunsen  for  many  years.  In 
1875,  however,  he  left  the  scene  of  his  brilliant  achievements,  and  went 
back  to  Berlin  to  serve  as  professor  of  physics  and  to  work  with 
Helmholtz.  He  died  on  October  17,  1887,  at  the  age  of  sixty-three  years. 

KirchhofFs  mind  was  more  speculative  than  Bunsen's,  he  had  greater 
fondness  for  pure  mathematics,  and  he  was  thoroughly  familiar  with  the 
researches  of  Sir  Isaac  Newton,  Joseph  Fraunhofer,  and  Rudolf  Clausius 
(8,  46).  He  showed  Bunsen  that,  instead  of  looking  through  colored 
glass  to  distinguish  between  similarly  colored  flames,  he  ought  to  use  a 
prism  to  separate  the  light  into  its  constituent  rays  (9).  On  this  principle 
they  developed  the  KirchhoflF-Bunsen  spectroscope,  an  instrument  which 
proved  to  be  of  supreme  importance  not  only  in  chemical  analysis,  but 
also  in  the  discovery  of  new  elements  (58). 

They  noticed  that  when  ordinary  salt  was  sprinkled  into  the  flame 
of  a  Bunsen  burner,  a  yellow  line  was  seen  through  the  spectroscope  in 
exactly  the  position  formerly  occupied  by  the  dark  double  line  of  the 
sun's  spectrum  known  as  the  D-line.  Attempting  then  to  observe  the 
dark  D-line  and  the  bright  sodium  line  simultaneously,  by  allowing 


SOME  SPECTKOSCOPIC  DISCOVERIES 


627 


Gustav  Robert  Kirchhoff,  1824-1887. 
German  physicist  and  physical  chem- 
ist. Professor  of  physics  at  Heidelberg 
and  Berlin.  Independent  discoverer  of 
the  Kirchhoff-Stewart  law  of  radiation 
and  absorption.  He  explained  the 
Fraunhofer  lines  of  the  solar  spectrum, 
and,  with  Bunsen,  founded  the  science 
of  spectroscopic  analysis  and  discovered 
the  elements  cesium  and  rubidium. 


sunlight  and  yellow  sodium  light  to  shine  on  the  slit  of  the  spectroscope 
at  the  same  tune.,  they  were  astonished  to  find  that  the  dark  line  did  not 
become  yellow?  but  became  darker  than  before.  Kirchhoff  was  so 
puzzled  by  this  that  he  spent  the  entire  day  and  night  trying  to  account 
for  it,  and  finally  succeeded  in  producing  the  dark  D-line  artificially. 
He  did  this  by  using,  instead  of  sunlight,  a  luminous  flame,  which  gives 
a  continuous  spectrum  containing  no  dark  lines,  and  then  bringing  the 
yellow  sodium  flame  in  front  of  the  slit  as  before.  Kirchhoff  gave  as 
his  explanation  the  analogy  of  sympathetic  vibrations.  The  white  light 
from  the  luminous  flame,  upon  passing  through  the  sodium  flame,  lost 
those  vibrations  which  correspond  to  the  yellow  lines,  and  therefore  the 
spectrum  contained  a  dark  line  at  that  place  (9,  34). 

On  April  11,  I860,  Bunsen  wrote,  "Don't  be  angry  with  me,  dear 
Roscoe,  if  I  have  still  done  nothing  more  on  our  photochemical  work/' 
and  explained  that  he  was  searching  for  a  new  alkali  metal  (9).  On 
November  6  of  the  same  year  he  wrote  again  to  Roscoe: 

I  have  been  very  fortunate  with  my  new  metal,  I  have  fifty  grams  of 
the  almost  pure  chlorplatinate,  which  I  can  easily  make  absolutely  pure.  To 
be  sure  these  fifty  grams  were  obtained  from  600  hundred  weights  (quintals) 
of  mineral  water,  whereby  21/2  pounds  of  lithium  chloride  were  obtained  as 
a  by-product.  Since  I  have  a  simple  method  of  separating  it,  I  find  it  widely 
distributed.  I  shall  name  it  cesium  because  of  its  beautiful  blue  spectral  line. 
Next  Sunday  I  expect  to  find  time  to  make  the  first  determination  of  its 
atomic  weight, 


628  DISCOVERY  OF  THE  ELEMENTS 


The   Kirchhoff-Bonsen   Spectroscope 


Bunsen  had  announced  this  discoveiy  to  the  Berlin  Academy  of  Sciences 
on  May  10,  1860  (8). 

In  one  of  their  papers  Bunsen  and  Kirchhoff  told  just  how  they 
traced  down  the  new  element: 

If  one  brings  into  the  flame  of  the  spectroscope  a  drop  of  mother  liquor 
from  the  Durkheim  mineial  water,  one  recognizes  only  the  characteristic  rays 
of  sodium,  potassium,  lithium,  calcium,  and  strontium  If  then,  after  having 
precipitated  by  known  methods  the  lime,  strontia,  and  magnesia,  one  takes  up 
the  residue  with  alcohol  previously  treated  with  mtiic  acid  to  fix  the  bases, 
one  obtains,  after  having  removed  the  lithia  by  means  of  ammonium  carbonate, 
a  mother  liquor  which  in  the  spectroscope  gives  the  lines  of  sodium,  potassium, 
and  lithium,  and,  in  addition,  two  remarkable  blue  lines,  very  close  together, 
one  of  which  coincides  almost  exactly  with  the  line  Sr  S. 

Now  there  is  no  simple  substance  known  which  gives  two  such  rays  in 
this  part  of  the  spectrum;  one  may  theiefore  conclude  the  certain  existence 
<of  a  simple  unknown  substance,  belonging  to  the  group  of  alkali  metals.  We 
propose  to  give  this  new  metal  the  name  cesium  (symbol  Cs)  from  caesius, 
which  the  ancients  used  to  designate  the  blue  of  the  upper  part  of  the 
firmament.  This  name  seems  to  us  to  be  justified  by  the  facility  with  which 
one  may  confirm,  by  the  beautiful  blue  color  of  the  incandescent  vapor  of  this 
new  element,  the  presence  of  a  few  milhonths  of  a  milligram  of  this  simple 
substance  mixed  with  soda,  lithia.,  and  strontia  (43  29,  SO) 

Other  chemists  had  examined  cesium  minerals  before  but  had  failed 
to  recognize  the  presence  of  the  new  metal.  August  Breithaupt  (1791- 
1873),  in  his  examination  of  some  corroded  quartzes  from  Elba  in  1846, 


SOME  SPECTROSCOPIC  DISCOVERIES  629 


(Left  to  right)  G.  Kirchhoff,  R.  W.  Bunsen,  and  H.  E.  Roscoe,  in  1802. 

Kirchlioff  and  Bunsen  invented  the  spectroscope  and  founded  the  science  of 

spectroscopic  analysis.     Roscoe  collaborated  with  Bunsen  in  photochemical 

researches,  and  was  the  first  to  prepare  metallic  vanadium. 


630 


DISCOVERY  OF  THE  ELEMENTS 


distinguished  two  closely  related  minerals  which  he  named  castor  (which 
was  afterward  shown  to  be  a  kind  of  petalite)  and  pollux,  which  was 
later  found  to  contain  cesium  (66,  67).  In  the  same  year  C.  F.  Plattner 
analyzed  the  latter  mineral  very  carefully,  but  his  results  added  up  to 
only  92.75  per  cent  (10,  36).  Although  he  made  special  tests  for  chlorine, 
fluorine,  and  other  substances  which  might  be  present  in  a  silicate,  his 
results  were  negative,  and  because  of  the  smallness  of  his  specimen  he 
was  unable  to  repeat  the  quantitative  analysis.  He  was  impressed  by 
the  fact  that  pollux  (poflucite)  had  a  higher  alkali  content  than  any 
silicate  previously  known  (36). 


Carl    Friedrich    Plattner,*    1800-1858. 

Professor  of  metallurgy  at  the  Freiberg 
School  of  Mines  Author  of  books  on 
blowpipe  analysis  and  the  roasting  of 
ores.  He  was  an  expert  analyst,  trained 
under  Heinrich  Rose  When  his  careful 
analysis  of  pollux  was  made  in  1846,  the 
spectroscope  had  not  yet  been  invented, 
and  he  was  unable  to  recognize  the 
presence  of  the  new  element  cesium 


Carl  Friedrich  Plattner  was  born  in  1800  at  Klein-Walters dorf  near 
Freiberg,  was  educated  at  the  Freiberg  School  of  Mines,  and  became  a 
professor  of  metallurgy  and  blowpipe  analysis  there.  He  was  a  great 
master  of  the  art  and  science  of  analytical  chemistry,  and  applied  the 
blowpipe  even  to  quantitative  analysis.  He  made  many  promising 
experiments  on  the  oxidation  of  sulfur  dioxide  to  the  trioxide  by  means 
of  catalysts.  Before  the  work  was  completed,  however,  he  was  stricken 
with  apoplexy,  which  terminated  fatally  in  1858  (68).  When  F£lix 
Pisani  (1831-1920)  examined  pollucite  four  years  after  the  discovery 
of  cesium,  he  found  that  Plattner  had  mistaken  his  cesium  sulf ate  for  a 
mixture  of  the  sulfates  of  sodium  and  potassium  (8.,  37,  58). 

*  The  portrait  of  Plattner  has  been  reproduced  from  F.   G.   Coming's  "A  Student 
Reverie"  by  land  permission  of  the  author. 


SOME  SPECTROSCOPIC  DISCOVERIES 


631 


PREFACE 


FOTTKTH 


at  the  paWisher'B  ?sqaesrlv  after  the  third  edition  of 
LOTTWE  ASALTSIS  was  a&autod*  I  undertook  the 
of  the  jpreeeafc  edition,  it  ma  in  tha  belief  that  now,  as 
upny  wonld  desire  to  haTe  at  hand  a  complete  manual 
BO  wscfol^pi'bjeot    M  fee  as  powiblfl  J  hate  coated  myself 

^^t  ~  i  fc 

to  tlie  p%Kma  labor?  of  raj  $to$FwikoTf  wiwm  I  «in  Jxerenr  fcsrget, 
havo  en]j  added  <rach  new  and  a^pioriad  matter  as  had  betfa 
kuuw|  EiDce,  the  appouamce  of  the  third  edition, 
had  aaff^a^pjpoartttni^r,,  ^oiij^g  iewtal  year9f^i  irh 
laWretl  as  a  fc^w&frr  of  tb^  6*WBOh  «C  sipaljftfa  is  a 

y,  t&  ^anvfnpe  hrojwJf  pf  ih*  (Ratable  iray  ^  ?r¥<i  th* 

rf  ^1    >^  J  T  ' 

fe  cjaswflod  flgid  treated  rn^Hl  Wuwfcf  '^  ^ 

'      *l  <.!„'*  k.  „,         «,  *    ',T 

this  Cfia^ j^SE&ia,  ^inff  as  'fifiow^  a  jreoeptwa  AS  hja  Iwea 


Plattner's  **Blowpipe  Analysis"  was  revised  by  his 
former  student,  Hieronymus  Theodor  Richter,  who, 
with  Ferdinand  Reich,  discovered  the  element  indium. 


Pisani  was  a  well  known  French-Italian  analytical  chemist  and 
mineral  dealer  who  taught  chemistry  and  did  consulting  analytical  work 
in  a  private  school  in  Paris  which  C.  F.  Gerhardt  had  formerly  conducted. 
He  lived  to  be  almost  ninety  years  old?  and  continued  his  researches  al- 
most to  the  time  of  his  death  (  58  )  . 


RUBIDIUM 

On  February  23,  1861,  only  a  few  months  after  the  discovery  of 
cesium,  Bunsen  and  Kirchhoff  announced  to  the  Berlin  Academy  the 
existence  of  another  new  alkali  metal  in  lepidolite. 

Klaproth  said  that  lepidolite,  the  first  source  of  rubidium,  was  dis- 
covered by  the  Abbe"  Nicolaus  Poda  of  Neuhaus  (1723P-1798),  a  Jesuit 


632  DISCOVERY  OF  THE  ELEMENTS 

scholar  and  member  of  the  hereditary  Austrian  nobility.  For  several 
years  he  lectured  on  mining  mechanics  and  surveying  at  the  School  of 
Mines  of  Schemnitz  (69}. 

The  first  published  account  of  lepidolite  (or  lilalite,  as  the  Abbe 
Poda  called  it)  is  Baron  von  Born's  descnption  of  a  specimen  from  Count 
Mittrowsky's  estate  at  Rozena,  Moravia,  which  appeared  in  CrelTs 
Annalen  in  1791,  just  after  Baron  von  Bern's  premature  death.  Count 
Johann  Nepomuk  von  Mittrowsky  (1757-1799)  of  Bystrzitz  and  Rozinka 
devoted  the  later  years  of  his  brief  life  entirely  to  science,  especially  to 
the  botany  and  mineralogy  of  Moravia  (69).  One  of  Baron  von  Born's 
last  researches  was  his  investigation  of  lepidolite.  When  he  ignited  it 
between  coals,  it  frothed,  and  fused  to  a  porous  slag.  When  he  heated 
it  strongly,  it  formed  a  dense  white  glass.  He  found  its  principal  con- 
stituent to  be  sihca  (70). 

Klaproth's  first  analysis  of  lepidolite  did  not  show  the  presence  of 
any  alkali.  When  he  examined  it  a  second  time,  however,  he  wrote: 
"Since  the  analysis  of  leucite,  described  in  the  earlier  part  of  this  work, 
has  evidently  proved  that  it  contains  the  vegetable  alkali  as  one  of  its 
essential  constituent  parts,  it  was  to  be  expected  that  this  alkaline  sub- 
stance might  likewise  be  found  in  the  mixture  of  various  other  species 
of  stones  and  earths.  The  first  confirmation  of  this  conjecture  has  been 
afforded  to  me  by  the  Lepidolite."  His  final  analysis  of  "the  amethystine 
red  lepidolite"  yielded  silica  54.50,  alumina  38.25,  potash  4,  oxides  of 
manganese  and  iron  0.75,  and  "loss,  partly  consisting  of  water"  2,50  per 
cent  ( 71 ) .  Klaproth's  analysis  failed  to  show  the  presence  of  two 
essential  constituents  of  lepidolite:  lithium  (which  had  not  yet  been  dis- 
covered) and  fluorine. 

In  1861  Robert  Bunsen  and  G.  R.  Kirchhoff  separated  the  alkalies 
from  some  lepidolite  from  Saxony  and  precipitated  the  potassium  with 
platinic  chloride.  After  they  had  washed  this  precipitate,  they  examined 
it  with  the  spectroscope  and  observed  two  new  lines  which  proved  to 
be  those  of  an  unknown  element,  which  they  named  rubidium.  The 
report  runs  as  follows: 

If  one  treats  lepidolite  from  Saxony  by  one  of  the  known  methods  which 
yield  a  solution  of  the  alkalies  separated  from  the  other  elements,  and  if  one 
pours  some  platinic  chloride  into  the  liquid,  one  obtains  an  abundant  precipitate 
which,  tested  in  a  spectroscope,  shows  only  the  lines  of  potassium 

If  one  washes  this  precipitate  several  times  with  boiling  water,  and  tests 
it  at  intervals  in  the  apparatus,  one  notices  two  new  lines  of  a  magnificent  violet 
located  between  the  lines  Sr  8  and  the  Ka  /?*  line  of  potassium.  As  the 
washing  is  continued,  these  lines  stand  out  more  and  more  against  the  con- 

*  Bunsen  and  Kirchhoff  used  the  symbol  Ka  for  potassium  (kalium),  instead  of  K. 


SOME  SPECXROSCOPIC  DISCOVERIES  633 

tinuous  spectrum  of  potassium,  which  fades  away.  Soon  one  sees  a  ceitam 
number  of  new  rays  in  the  red,  the  yellow,  and  the  green.  None  of  these 
lines  belong  to  elements  hitherto  discoveied  Among  them  we  may  mention 
especially  two  remarkable  red  lines  just  beyond  the  bulliant  Fraunhofer  line 
A,  or,  if  one  prefers,  the  brilliant  Ka  line  which  corresponds  to  it,  which 
ray  is  located  at  the  extreme  led  end  of  the  solar  spectrum.  The  magnificent 
dark  red  color  of  these  rays  of  the  new  alkali  metal  led  us  to  give  this  element 
the  name  rubidium  and  the  symbol  Kb  from  rubidus,  which,  with  the  ancients, 
served  to  designate  the  deepest  red  (4,  30,  31,,  35). 

The  colorless  flame  of  the  burner  which  Buiisen  perfected  in  1854-55 
made  this  research  possible. 

Although  Bunsen  succeeded  in  isolating  rubidium  (42),  he  observed 
cesium  only  by  means  of  its  spectral  lines  (41).  Twenty  years  later  Dr. 
Carl  Setterberg  succeeded  in  isolating  cesium  by  electrolysis  of  the 
cyanide  in  presence  of  barium  cyanide.  The  electrolytic  part  of  the 
research  was  performed  in  Bunsen's  laboratory. 

When  the  five-hundredth  anniversary  of  Heidelberg  University  was 
celebrated  in  1886,  an  elaborate  breakfast  was  served  which  lasted  more 
than  three  hours.  Bunsen  fell  asleep  during  one  of  the  tiresome  speeches, 
but  at  one  place  in  the  address  the  speaker's  loud  oratory  caused  the 
aged  chemist  to  awake  with  a  start  Rubbing  his  eyes,  he  whispered  to 
his  neighbor,  "I  thought  I  had  let  a  test-tube  full  o£  rubidium  fall  to  the 
floor"*  (11). 

On  another  occasion  an  Englishwoman,  to  whom  he  had  just  been 
introduced,  mistook  him  for  Josias  Bunsen,  the  ambassador,  and  asked 
him  if  he  had  finished  his  book  entitled  "Gott  in  der  Geschichte."  "Alas," 
replied  Bunsen,  "My  untimely  death  prevented  me"1"  (H). 

Robert  Bunsen  was  one  of  the  most  modest  of  men.  When  he 
found  it  necessary  to  mention  his  own  discoveries  in  his  lectures,  he  never 
said,  "I  have  discovered/'  but  always  "Man  hat  gefunden."  However, 
when  the  lecture  dealt  with  spectral  analysis,  his  students  showed  by 
prolonged  applause  that  they  understood  and  were  proud  of  his  great 
achievements.  Bunsen  won  many  honors  and  medals,  but  of  these  he 
once  said  sadly,  "Such  things  had  value  for  me  only  because  they  pleased 
my  mother;  she  is  now  dead"*  (12,  49). 

Like  N.-L.  Vauquelin  and  Henry  Cavendish,  Bunsen  never  married, 
and,  when  asked  for  the  reason,  he  used  to  say,  "I  never  could  find  the 
time."  Perhaps  this  lack  of  family  ties  made  his  students  even  more  dear 

*  Mir  war  als  hatte  tch  ein  Probierrohrchen  mit  Rubidium  auf  den  Boden  fallen  lassen. 
t  Ach  daran  hat  mich  ja  mem  friihzeitiger  Tod  verhmdert. 

*  Solche  Dmge  batten  nur  Werth  fur  mich,  well  sie  meine  Mutter  erfreuten;  sie 
ist  nun  todt. 


634 


DISCOVERY  OF  THE  ELEMENTS 


Hermann  (Ludwig  Ferdinand)  von 
Helmholtz,  1821-1894.  Professor  of 
physiology  at  Bonn  and  at  Heidelberg. 
Professor  of  physics  at  Berlin.  Inventor 
of  the  ophthalmoscope,  an  instrument  for 
examining  the  retina  of  the  eye.  He  ex- 
pressed the  principle  of  the  conservation 
of  energy  in  mathematical  form 


to  him,  for  he  used  to  work  all  day  In  the  laboratory,  patiently  showing 
them  the  fine  details  of  chemical  manipulation.  When  he  was  seventy 
years  old,  he  wrote  to  Roscoe,  "In  the  years  which  I  am  rapidly  approach- 
ing, one  lives  more  in  the  recollection  of  past  happy  days  than  in  the 
present;  and  to  the  most  pleasure-giving  of  them  belong  those  which  for 
many  years  we  spent  in  true  friendship  together."  After  his  long  day's 
work,  his  favorite  recreation  was  to  go  walking  over  the  chestnut-wooded 
hills  near  Heidelberg  in  company  with  a  friend  like  Kirchhoff  or  Hermann 
vonHelmholtz  (13). 

Bunsen  was  blessed  with  a  brilliant  mind,  a  happy  disposition,  a 
strong,  healthy  body,  and  a  long  life  (48).  He  was  seventy-six  years 
old  when  he  invented  the  vapor  calorimeter,  and  after  he  retired  from  his 
Heidelberg  professorship  at  the  age  of  seventy-eight,  he  still  had  ten 
years  to  live.  These  last  days  were  brightened  by  the  honor  and  respect 
paid  him  by  his  former  students  and  colleagues.  Sir  Henry  Roscoe  said 
that  during  the  peaceful  sleep  in  which  Bunsen  lay  for  three  days  preced- 
ing his  death  on  August  16,  1899,  his  face  retained  "the  fine  intellectual 
expression  of  his  best  and  brightest  days"  (13 ) , 

After  the  brilliant  researches  of  Bunsen  and  Kirchhoff  had  paved 
the  way,  other  new  elements  were  soon  revealed  by  the  spectroscope. 
Among  these  may  be  mentioned  thallium,  indium,  gallium,  helium, 
ytterbium,  holmium,  thulium,  samarium,  neodymium,  praseodymium, 
and  lutetium. 


SOME  SPECTROSGOPIC  DISCOVERIES  635 


Bunsen  Memorial  in  Heidelberg 


THALLIUM 

The  first  indication  of  the  existence  of  thallium  was  noted  by 
Sir  William  Crookes.  Sir  William  was  bom  on  June  17,  1832,  and  was 
educated  in  the  grammar  school  at  Chippenham.  At  the  age  of  sixteen 
years  he  entered  the  Royal  College  of  Chemistry.,  where  A.  W.  von 
Hofmann  was  serving  as  the  first  professor;  yet  in  spite  of  the  latter's 
inspiring  influence,  he  never  cared  for  organic  chemistry.  His  first  paper 
entitled  ecOn  the  Selenocyanides"  was  published  when  he  was  nineteen 
years  of  age.  In  1859  he  started  the  publication  of  Chemical  News,  and 
until  1906  he  was  the  sole  editor  of  that  important  journal  (14). 

One  day,  very  soon  after  Bunsen  and  Kirchhoff  had  announced  their 
discovery  of  rubidium,  Crookes  happened  to  examine  some  residues  from 
a  sulfuric  acid  plant  at  Tilkerode  in  the  Harz.  Hofmann  had  given  him 
these  residues  some  years  before,  because  they  contained  selenium  com- 
pounds which  could  be  converted  into  selenocyanides;  and,  after  remov- 
ing the  selenium,  Crookes  had  saved  them  because  he  thought  they  also 
contained  tellurium. 

When  he  examined  the  residues  with  the  spectroscope,  however, 
he  found  no  lines  of  tellurium,  and  the  lines  of  selenium  soon  faded 
out.  Soon  there  appeared  a  beautiful  green  line  that  he  had  never  seen 


636 


DISCOVERY  OF  THE  ELEMENTS 


before.  He  concluded  that  the  material  must  contain  a  new  element, 
and  because  of  the  green  line  in  the  spectrum  he  named  it  thallium,  or 
green  branch.  In  his  first  announcement,  which  appeared  in  the  Chem- 
ical News  on  March  30,  1861  (38),  Sir  William  Crookes  stated:  "In  the 
year  1850  Professor  Hofmann  placed  at  my  disposal  upwards  of  ten 
pounds  -of  the  seleniferous  deposit  from  the  sulfuric  acid  manufactory 
at  Tilkerode,  m  the  Harz  Mountains,  for  the  purpose  of  extracting  from 
it  the  selenium,  which  was  afterwards  employed  in  an  investigation  upon 
the  seleno-cyanides.  Some  residues  which  were  left  in  the  purification 
of  the  crude  selenium,  and  which,  from  their  reactions,  appeared  to  con- 
tain tellurium,  were  collected  together  and  placed  aside  for  examination 
at  a  more  convenient  opportunity.  .  .  . 


August  Wilhelm  von  Hofmann,  1818- 
1892.  German  chemist  who  served  for 
many  years  as  the  first  professor  at  the 
Royal  College  of  Chemistry  in  London 
Founder  of  the  aniline  dye  industry 
He  devised  the  simple  process  of  pre- 
paring aniline  by  nitrating  benzene  and 
reducing  the  nitrobenzene.  He  was  one 
of  the  founders  of  the  Deutsche  Chem- 
ische  Gesellschaft,  and  was  elected 
president  fourteen  times.  See  also  ref. 
(65). 


From,  Muspratt's  "Chemistry,  Theoretical^ 
Practical,  and  Analytical" 


"It  was  not  until  I  had  in  vain  tried  numerous  chemical  methods  for 
isolating  the  tellurium  which  I  believed  to  be  present,  that  the  method  of 
spectrum  analysis  was  used.  A  portion  of  the  residue  introduced  into 
a  gas-flame  gave  abundant  evidence  of  selenium;  but  as  the  alternate 
light  and  dark  bands  due  to  this  element  became  fainter,  and  I  was 
expecting  the  appearance  of  the  somewhat  similar  but  closer  bands  of 
tellurium,  suddenly  a  bright-green  line  flashed  into  view  and  quickly 
disappeared"  (38),  Although  he  at  first  believed  thallium  to  be  a  non- 
metal  similar  to  sulfur,  he  soon  changed  his  mind,  and  in  1862  he  was 


SOME  SPECTROSCOPIC  DISCOVERIES 


637 


awarded  a  prize  for  some  specimens  labeled  "Thallium,  a  new  metallic 
element,"  which  he  exhibited  at  the  International  Exhibition  (14). 

Sir  William  Crookes  will  probably  be  longest  remembered  for  his 
study  of  rarefied  gases  and  for  his  discoveries  in  radioactivity  and 
molecular  physics.  After  Sir  William  Ramsay  discovered  helium  in  1895, 
it  was  Crookes  who  established  its  identity  with  the  helium  that  Sir 
Norman  Lockyer  had  observed  spectroscopically  in  the  sun's  atmosphere. 
Crookes  also  invented  the  radiometer  and  the  spinthariscope.  As  early 
as  1886-88  he  recognized  the  existence  of  atomic  species  of  identical 


Sir  William  Crookes,  1832- 
1919,  English  physicist  and 
chemist  Professor  at  the  Royal 
College  of  Chemistry.  Inventor 
of  the  radiometer  and  the 
spinthariscope  Founder  and 
editor  of  Chemical  News.  He 
was  the  first  to  observe  the  green 
line  of  thallium  and  the  first  to 
prove  the  identity  of  solar  and 
terrestrial  helium.  The  discov- 
erer of  uranium  Xi. 


Courtesy  Lyman  C.  Neivell 


chemical  properties  but  different  atomic  weights,  which  he  called  "meta- 
elements,"  and  thus  came  close  to  the  modern  concept*  of  isotopes  (59, 
60).  While  serving  on  the  Glass  Workers'  Cataract  Committee  of  the 
Royal  Society,  he  carried  out  practical  research  of  great  humanitarian 
value.  He  prepared  a  kind  of  glass  which,  although  nearly  colorless, 
cut  off  the  injurious  rays  from  the  white-hot  molten  glass,  and  protected 
the  eyes  of  the  workers  (14),  On  two  occasions  Sir  William  visited  the 


638  DISCOVERY  OF  THE  ELEMENTS 

famous  diamond  mines  at  Kimberley,  and  in  1909  he  wrote  a  little  book 
on  diamonds,  which  he  dedicated  to  his  wife. 

Charles  Baskerville  once  wrote  a  biographical  sketch  of  Crookes,  in 
which  he  gave  the  following  pleasing  description  of  his  home  (15) : 

Sunday  evenings  Sir  William  is  at  home.  Within  his  study  walls,  be- 
booked  to  the  ceiling,  one  may  find  then  the  finest  minds  of  science  in  England 
or  in  other  lands,  grappling  m  discussion  with  the  unsolved  problems,  which 
oftentimes  become  no  clearer  than  the  increasing  denseness  of  the  tobacco 
smoke.  Promptly  at  eleven  o'clock  there  comes  a  bright  rift  in  the  clouds 
as  Lady  Crookes  enters  and  charmingly  leads  all  to  the  dining-room  below. 
Punctilious  in  the  performance  of  every  duty,  courteous  but  vigorous  in 
argument,  modestly  assertive,  learning  from  the  youngest,  Sir  William  draws 
out  the  humblest  until  he  would  become  almost  bold,  yet,  in  return,  he  gives 
generously  from  his  rich  store  of  wide  knowledge  and  large  experience. 

After  Lady  Crookes  died  in  1916  Sir  William  never  recovered  from  his 
loss.  He  died  on  April  4,  1919,  at  the  age  of  eighty-six  years  (14). 

Although  there  seems  to  be  no  doubt  that  Sir  William  Crookes  was 
the  first  to  observe  the  green  line  of  thallium,  many  chemical  historians, 
especially  the  French  ones,  attribute  the  isolation  of  the  metal  itself  to 
Claude-Auguste  Lamy.  He  was  born  on  July  15,  1820,  at  Nery  in  the 
Jura  department  of  France,  attended  the  ficole  Normale  Sup^rieure  in 
Paris,  and  at  the  age  of  thirty-one  years  received  his  doctorate  from  Lille, 
He  taught  physics,  first  at  Limoges  and  later  at  Lille  (16). 

C.-A.  Lamy  first  observed  the  green  line  of  thallium  in  March, 
1862,  in  a  sample  of  selenium  which  his  brother-in-law  M.  Fr6d6ric 
Kuhlmann  had  extracted  from  the  slime  in  the  lead  chambers  of  a  plant 
where  sulfuric  acid  was  made  by  burning  pyrite.  On  June  23,  1862, 
he  presented  a  14-gram  ingot  of  thallium  metal  to  the  Academie  des 
Sciences.  He  stated  that  thallium  exists  in  several  kinds  of  pyrite  used 
for  the  manufacture  of  sulfuric  acid,  including  the  Belgian  pyrites  of 
Theux,  Namur,  and  Philippeville  and  some  mineralogical  specimens  from 
Nantes  and  Bolivia.  He  found  it  much  easier  to  extract  the  thallium 
from  the  slime  in  the  lead  chambers  than  from  the  pyrite.  Lamy's 
method  of  isolating  thallium  may  best  be  described  in  his  own  words: 

When  burned  in  suitable  pits,  pyrite  yields,  among  other  products,  sulfur 
dioxide,  arseniouS  and  selenious  acids,  and  the  oxide  of  thallium,  which 
are  carried  over  into  the  first  lead  chamber,  with  the  ferruginous  dust.  In  this 
first  chamber,  especially  if  it  has  no  other  communication  with  the  following 
ones  than  the  gas  pipe,  the  oxide  of  thallium  deposits  and  accumulates,  and 
finally  thallium  sulfate,  with  sulfates  of  lead,  iron,  and  other  foreign  substances 
coming  from  the  pyrite. 


SOME  SPECTROSCOPIC  DISCOVERIES 


639 


The  thallium  [continued  Lamy]  is  extracted  from  these  deposits  in  the 
first  chamber.  When  these  deposits  are  heated  almost  dry,  with  approximately 
an  equal  volume  of  aqua  regia,  until  the  acid  almost  disappears,  and  the  mass 
is  then  taken  up  with  twice  its  weight  of  boiling  water,  one  sees  formed  in 
the  liquid  as  it  cools  an  abundance  of  yellow  crystalline  plates  which,  when 
purified  by  several  successive  recrystallizations,  give  a  magnificent  compound 
of  thallium  sesquichloride.  When  this  chloride  is  submitted  to  the  decom- 
posing action  of  the  electric  current  from  four  or  five  Bunsen  cells,  for  example, 
there  appears  at  the  negative  pole  pure  thallium  This  is  the  experiment  by 
which  we  have,  for  the  first  time,  isolated  the  new  metal  (17,  89). 


Claude-Auguste  Lamy,  1820-1878. 
President  of  the  Soci&te  Chimique  de 
France  in  1873  The  first  person  to 
prepare  an  ingot  of  metallic  thallium. 
He  made  a  thorough  study  of  its  com- 
pounds and  proved  that  they  are 
poisonous  Author  of  many  papers  on 
optics,  electricity,  pyrometry,  organic 
and  inorganic  chemistry,  and  sugar 
technology. 


From  "Cinquantenaire  de  la 
Soci&£  Chtmique  de  France" 


Although  Lamy  claimed  that  Sir  William  Crookes's  thallium  was 
really  a  sulfide,  the  latter  replied  that  he  had  prepared  metallic  thallium 
as  early  as  May  1,  1862,  but  that  because  of  its  volatility  he  had  not  dared 
to  melt  the  black  powder  to  form  an  ingot  (18).  However,  a  com- 
mittee from  the  French  Academy,  including  Henri  Sainte-Claire  Deville, 
Th^ophile-Jules  Pelouze,  and  J.-B.-A.  Dumas,  credited  Lamy,  rather 
than  Crookes,  with  the  isolation  of  thallium  metal  (17,  40). 

After  a  careful  study  of  the  chemical  compounds  of  the  new  metal. 
Professor  Lamy  concluded  that  it  forms  two  series  of  salts,  the  thallous 
and  the  thallic,  in  which  the  metal  is  respectively  mono-  and  trivalent. 
Since  the  thallous  compounds  resemble  those  of  the  alkali  metals, 
whereas  tie  thallic  salts  are  similar  to  those  of  aluminum,  Dumas  once 


640 


DISCOVERY  OF  THE  ELEMENTS 


said,  "It  is  no  exaggeration  to  say  that  from  the  point  of  view  of  the 
classification  generally  accepted  for  the  metals,  thallium  offers  a  com- 
bination of  contradictory  properties  which  would  entitle  one  to  call  i1 
the  paradoxical  metal,  the  oniithorhynchus  of  the  metals"*  (40,  47). 

In  1865  Lamy  became  a  professor  of  chemistry  at  the  Central  School 
of  Arts  and  Manufactures  at  Paris.  He  published  papers  on  magnetism, 
the  progress  of  physics,  the  toxic  effect  of  thallium,  and  the  solubility 
of  lime  in  water.  He  died  at  Paris  on  March  20,  1878  (16). 


Jean  Baptiste-Andre"  Dumas, 
1800-1884.  Professor  of  chem- 
istry at  the  Athenaeum  and  at 
the  Sorbonne.  He  devised  a 
method  of  determining  vapor 
density,  and  developed  the 
theory  of  types  in  organic  chem- 
istry, which  he  defended  against 
Berzehus*  duahstic  electrochem- 
ical theory.  From  a  study  of 
the  aliphatic  alcohols,  Dumas 
and  Pehgot  developed  the  con- 
ception of  homologous  series. 
See  also  re£.  (62). 


Courtesy  Lyman  C   Newell 


In  1863  R.  C.  Bottger  of  Frankfort-on-the  Main  found  that  thallium 
occurs  ia  some  spring  waters.  A  certain  salt  mixture  from  Nauheim 
contained,  in  addition  to  the  chlorides  of  sodium,  potassium,  and  mag- 
nesium, those  of  cesium,  rubidium,  and  thallium.  Since  he  was  able 
to  prepare  a  thallium  ferric  alum  exactly  analogous  to  potassium  ferric 
alum,  he  regarded  thallium  as  an  alkali  metal  (72,  73).  Although  it  is 
sometimes  univalent  like  sodium  and  potassium,  it  is  now  classified 
in  Group  III  of  the  periodic  system. 

**  "ll  n'y  a  pas  d'exageration  d  dire  quau  point  de  vue  de  la  classification  g&n&alement 
accept&e  pour  les  in&taux,  le  thallium  offre  une  reunion  de  proprietes  contradictoires 
qui  autoriserait  &  Vappeler  le  m&tal  paradoxal,  I'ornithorynche  des  metaux." 


SOME  SPECTROSCOPIC  DISCOVERIES  641 

Grookesite,  a  Thallium  Mineral.  When  Baron  Nils  Adolf  Erik 
Nordenskiold  analyzed  specimens  of  the  selenium  minerals  eucairite  and 
berzelianite  from  Skrikerum,  Sweden,  in  1866,  he  detected  thallium  in 
both  of  them.  On  examining  the  specimens  in  the  Royal  Museum,  he 
found  a  new  mineral  which  C.  G.  Mosander  had  regarded  as  copper 
selenide  but  which,  on  analysis,  proved  to  be  a  rare  selenide  of  silver, 
copper,  and  thallium.  Baron  Nordenskiold  named  it  crookesite  in  honor 
of  the  discoverer  of  thallium,  and  for  many  years  it  was  the  only  known 
mineral  containing  thallium  as  an  essential  constituent  Nordenskiold 
described  it  as  a  mineral  forming  compact,  lead-gray  masses  with  a 
metallic  luster;  resembling  chalcocite  in  hardness;  and  having  a  specific 
gravity  of  6.9.  It  melts  easily  before  the  blowpipe  to  form  a  dark 
green  pellet,  colors  the  flame  an  intense  green,  and  is  insoluble  in 
hydrochloric  acid  but  readily  soluble  in  nitric  acid  (74,  75). 

Thallium  in  Pi/rite.  In  1867  Dr.  E.  Carstanjen  found  that  the  flue 
dust  from  the  pyrite-roasting  kilns  of  L,  Rdhr's  sulfuric  acid  plant  at 
Oranienburg  was  unusually  rich  in  thallium.  It  yielded  on  analysis 
3.5  per  cent  of  metallic  thallium.  By  working  up  a  large  quantity  of 
flue  dust  from  several  kilns,  he  prepared  twenty  or  thirty  pounds  of 

the  metal. 

In  an  attempt  to  trace  out  the  source  of  the  thallium  in  nature, 
Carstanjen  found  that  the  pyrite  had  come  from  rich  deposits  near  the 
village  of  Meggen  in  Siegerland,  Germany.  On  examining  the  pyrite 
in  this  locality  with  a  lens,  he  saw  some  small  black  specks  with  a  dull 
luster.  Specimens  of  pyrite  which  contained  these  specks  gave  a  distinct 
reaction  for  thalh'um  (76).  In  the  1866  edition  of  his  "Mineralogische 
Studien,"  August  Breithaupt  mentioned  a  pyrite  from  Grosskamsdorf 
near  Saalfeld,  Thuringia,  which  H.  T.  Richter  had  found  to  be  unusually 
rich  in  thallium  (77). 

Effect  of  Thallium  on  Plants  and  Animals.  On  January  29,  1863, 
R.  C.  Bottger  announced  that  he  had  detected  spectroscopic  traces  of 
thallium  in  wine,  chicory,  tobacco,  sugar  beet,  and  beech  wood,  and  had 
concluded  that  it  must  be  widely  diffused  in  the  vegetable  kingdom 
(47,  73).  Because  of  the  toxicity  of  thallium  compounds,  they  are 
sometimes  added  in  small  concentrations  to  the  soil  of  rodent-infested 
fields.  Too  high  a  concentration  of  thallium  inhibits  germination,  growth 
rate,  and  chlorophyll  formation  in  the  crops,  especially  in  rainy  weather 
(78). 

INDIUM 

In  1863  Ferdinand  Reich,  a  professor  of  physics  at  the  famous  School 
of  Mines  at  Freiberg,  and  his  assistant,  Hieronymus  Theodor  Richter, 


642 


DISCOVERY  OF  THE  ELEMENTS 


Ferdinand  Reich,  1799-1882.  Professor 
of  physics  and  inspector  at  the  Freiberg 
School  of  Mines  Discoverer  of  indium 
He  studied  the  deviations  in  the  declina- 
tion of  the  magnetic  needle,  the  rainfall 
and  snowfall  in  Freiberg,  and  the  tem- 
perature of  the  rocks  at  different  depths. 


discovered  the  element  indium.  The  former  was  born  at  Bernburg 
on  February  19,  1799,  and  was  educated  at  Leipzig,  Freiberg,  Gbttingen, 
and  Paris. 

In  1822  he  went  on  foot  to  Gottingen  to  study  chemistry  under 
Friedrich  Stromeyer,  whom  he  admired  "because  of  his  clarity  and  his 
appropriate  choice  of  material"  ( 51 ) ,  and  at  the  request  of  the  Freiberg 
authorities  he  selected  apparatus,  minerals,  and  rare  books  for  the  Mining 
Academy.  In  the  following  year  he  was  sent  to  Paris  on  a  similar  mission, 
and  returned  with  platinum  ware,  certified  weights,  apparatus,  and 
minerals  for  the  Freiberg  Academy  and  for  Stromeyer  in  Gottingen. 
While  in  Paris  he  studied  at  the  Sorbonne,  the  School  of  Mines,  and  the 
College  de  France,  and  met  Alexandre  Brongniart,  D.-F.  Arago,  L.-J. 
Gay-Lussac,  L.-J.  Thenard,  Justus  von  Liebig,  Elie  de  Beaumont,  and 
Alexander  von  Humboldt.  He  especially  admired  Gay-Lussac  "because 
of  his  modest  simplicity,  his  thoroughness,  and  the  wealth  of  his  knowl- 
edge" (51). 

From  1824  until  his  retirement  in  1866  Reich  served  as  inspector 
of  the  academy,  and  had  charge  of  the  mineral  collections,  purchase 
of  supplies,  keeping  of  records,  cataloging  of  the  library,  and  the 
editing  of  a  mining  and  metallurgical  calendar.  He  made  an  extended 
study  of  the  deviations  in  the  declination  of  the  magnetic  needle,  anc7 
for  many  years  kept  an  accurate  record  of  the  rainfall  and  snowfall  in 
Freiberg.  Soon  after  his  return  from  Paris  he  began  to  lecture  on  the 
French  system  of  weights  and  measures,  and  the  metric  system  was 
first  introduced  into  Saxony  by  Reich,  S.  A.  W.  Herder,  and  Brendel. 


SOME  SPECTROSCOPIG  DISCOVERIES  643 


Chemical  Laboratory  at  the  Freiberg  School  of  Mines 


Reich's  observations  of  the  temperatures  of  the  rocks  at  different  depths 
were  of  great  scientific  interest,  and  his  results  for  the  mean  density  of 
the  earth  were  in  good  agreement  with  those  of  Henry  Cavendish. 

In  the  winter  of  1830—31  Reich  gave  a  continuation  course  of 
private  lectures  before  about  sixty  educated  citizens  of  Freiberg,  most 
of  whom  were  connected  with  the  mines  and  smelters.  Although  these 
lectures  added  to  his  income,  he  discontinued  them  because  they 
necessarily  had  to  be  less  scientific  than  those  designed  for  his  regular 
students.  For  twelve  years  he  also  lectured  on  mineralogy,  and  for 
many  years  he  had  charge  of  the  course  in  general  chemistry. 

Since  Reich  was  always  deeply  concerned  about  the  welfare  of 
his  students  and  set  apart  a  special  evening  for  entertaining  them, 
they  regarded  him  as  a  true  friend.  He  occasionally  gave  private 
lectures  in  French  for  foreign  students  who  had  difficulty  with  the 
German  language. 

Smelter  fumes  which  damaged  crops,  fodder,  and  stock  were  a 
serious  problem.  While  Professor  Carl  Friedrich  Plattner  was  studying 
means  of  removing  sulfur  dioxide,  Reich  devised  a  simple  apparatus 
for  determining  the  sulfur  dioxide  content  of  vapors  and  gases.  Even 
the  erection  at  Hilbersdorf  of  the  tallest  smokestack  in  Europe  failed 


644 


DISCOVERY  OF  THE  ELEMENTS 


Hieronymus    Theodor    Richter,    1824- 

1898.  Director  of  the  Freiberg  School 
of  Mines  The  first  to  observe  the 
characteristic  blue  spectral  lines  of 
mdium  Metallurgist,  assayer,  and 
authority  on  blowpipe  analysis 


to  overcome  the  difficulty,  for  the  damage  to  fruits  and  trees  then 
extended  over  a  wider  area  than  before*  Although  Professor  Reich 
studied  the  fumes  in  forty  smelters  and  chemical  plants  in  Germany, 
Belgium,  and  England,  the  problem  was  not  settled  until  after  his 
death,  when  m  1890  a  tall  smokestack  was  erected  at  Halsbrucke  ( 51 ) . 

In  1863  Reich  began  a  search  for  thallium  in  some  Freiberg  zinc 
ores  from  the  Himmelsfiirst  mine  consisting  mainly  of  arsenical  pyrites, 
blende,  lead  glance,  silica,  manganese,  copper,  and  small  amounts  of 
tin  and  cadmium  (19,  43).  After  roasting  the  blende  to  remove  most 
of  the  sulfur  and  arsenic,  he  decomposed  it  with  hydrochloric  acid 
(47).  When  Clemens  WinHer,  who  was  then  a  metallurgist  in  the 
Saxon  smalt  works,  visited  Professor  Reich  in  1863,  the  latter  showed 
him  a  straw-yellow  precipitate  and  said,  "This  is  the  sulfide  of  a 
new  element3*  (52).  Because  of  his  colorblindness.,  however,  Reich 
entrusted  the  spectroscopic  examination  to  his  assistant,  Richter. 

Hieronymus  Theodor  Richter  was  born  at  Dresden  on  November 
21,  1824.  He  became  a  metallurgical  chemist  at  the  Freiberg  School 
of  Mines.  When  he  placed  some  of  the  zinc  blende  in  the  loop  of  a 
platinum  wire  and  heated  it  in  the  flame  of  a  Bunsen  burner,  he 
observed  a  brilliant  indigo  line  which  did  not  coincide  with  either  of 
the  blue  lines  of  cesium  (20,  52).  Because  of  this  characteristic  spectral 
line  the  new  element  was  christened  indium.  The  publication  of  this 
contribution  under  joint  authorship  was  a  mistake  which  Professor 
Reich  afterward  regretted,  for  Richter  tried  to  make  it  appear  that  he 
was  the  sole  discoverer  (2y  51,  5%), 


SOME  SPECTROSCOPIC  DISCOVERIES 


645 


Group  of  Rocks  at  the  Freiberg  School  of  Mines. 


Reich  and  Richter  found  later  that  there  are  two  indium  lines, 
the  brighter  one  being  slightly  more  refrangible  than  the  blue  line 
of  strontium,  and  the  weaker  one  still  more  refrangible  and  located 
near  the  blue  line  of  calcium.  Indium  compounds  impart  such  a 
brilliant  indigo-violet  color  to  the  Bunsen  flame  that  they  can  be 
recognized  even  without  a  spectroscope. 

They  separated  the  chloride  and  hydrated  oxide  of  indium  in 
small  amounts,  and,  by  cautiously  heating  a  mixture  of  indium  oxide 
and  sodium  carbonate  on  charcoal  by  means  of  a  blowpipe,  they  also 
obtained  some  impure  metal  (21,  43).  Metallic  indium  is  a  white, 
ductile,  easily  fusible  metal  like  tin,  and  it  leaves  a  mark  when  drawn 
across  paper. 

Reich  and  Richter  found  that  it  is  easier  to  isolate  it  from  the  zinc 
than  from  the  original  blende.  They  reduced  indium  oxide  in  a 
current  of  hydrogen  or  illuminating  gas  and  melted  the  metal  under 
potassium  cyanide  (44,  45}.  At  the  suggestion  of  Ferdinand  Reich, 
Clemens  Winkler  made  a  thorough  study  of  the  metal  and  its  com- 
pounds (20). 

In  Wells's  "Annual  of  Scientific  Discovery"  one  finds  an  interesting 
description  of  the  first  metallic  indium: 

Two  specimens  of  indium  were  exhibited  at  the  Academic  des  Sciences 
in  April,  1867,  by  Richter  They  were  prisms,  each  about  four  inches  long, 
the  section  being  that  of  a  trapezium  with  a  height  of  one-half  inch  and  with 
bases  respectively  1/2  inch  and  3/4  inch  in  breadth.  The  metal  was  very 


646  DISCOVERY  OF  THE  ELEMENTS 

pure  and  resembled  cadmium;  and  Richter  valued  these  two  specimens  at 
£.800 


Professor  Reich  took  no  part  in  political  life,  and  his  excellent 
library  contained  no  books  on  that  subject.  For  a  few  years,  however, 
he  served  as  commissioner  of  the  poor,  and  always  acted  for  the  best 
interests  of  those  in  need.  Although  he  had  no  children  of  his  own, 
Reich  helped  to  support  and  educate  the  eleven  children  of  his  unfor- 
tunate brother  Ludwig,  who  had  lost  both  wife  and  fortune.  Some  of 
the  nieces  lived  for  years  at  the  home  of  Professor  and  Mrs.  Reich,  and 
one  nephew  received  his  gymnasium  and  university  education  through 
their  generosity  (51). 

Reich  loved  to  travel,  and  even  in  his  boyhood  days  he  kept  a 
detailed  diary  of  all  his  trips.  After  his  retirement  at  the  close  of  1865 
he  bought  a  little  house,  where  he  lived  for  more  than  twenty  years, 
spending  much  time  wili  his  scientific  journals  and  books.  After  the 
death  of  his  wife  in  1876,  a  grandniece  kept  house  for  him  until  his 
death  on  April  27,  1882. 

In  1875  Richter  became  director  of  the  Freiberg  School  of  Mines 
His  American  student,  LeRoy  Wiley  McCay,  describes  him  as  "a 
nervous,  high-strung,  mobile  little  man."  He  was  expert  in  metallurgy 
and  assaying,  and  revised  some  of  the  later  editions  of  Plattner  s  "Blow- 
pipe Analysis/'  One  of  his  papers  was  on  the  extraction  of  gold  from 
gold  ores  with  chlorine  water,  He  was  most  exacting  with  his  students, 
who,  nevertheless,  enjoyed  his  unfailing  good  humor  and  bright  flashes 
of  wit  (20).  Richter  died  at  Freiberg  on  September  25,  1898  (16). 

Rudolph  Christian  Bottger  (1806-1881)  found  in  1866  that  the 
flue  dust  which  condensed  in  the  chimneys  of  the  zincworks  near  Goslar 
contained  about  one  part  of  indium  oxide  in  one  thousand  (79).  He 
perfected  methods  of  preparing  the  rare  metals  indium,  thallium,  and 
cesium  (80). 

Indium,  like  cadmium,  was  first  discovered  in  substances  of  which 
it  is  only  a  non-essential  constituent.  Clemens  Winkler  said  in  1867, 
"True  indium  minerals  have  not  yet  been  discovered.  So  far  as  I 
know,  indium  has  been  detected  up  to  the  present  only  in  a  few  zinc 
blendes:  in  those  of  Freiberg,  the  spectral-analytical  investigation  of 
which  led  to  the  discovery  of  the  new  metal,  and  in  the  black 
blende,  or  christophite,  of  Breitenbrunn  in  Saxony,  which  I  analyzed 
at  the  request  of  Mining  Superintendent  Breithaupt  and  found  to 
contain  0.0062  per  cent  of  indium.  However,  I  could  not  detect  indium 
in  black  blende  of  Turcz,  Hungary,  which  is  closely  related  to  christo- 
phite, nor  in  Silesian  calamine  and  the  zinc  and  cadmium  obtained 
from  it.  Bottger  finally  found  indium  in  the  flue  dust  of  the  zinc 


SOME  SPECTROSCOPIC  DISCOVERIES  647 

roasting  kilns  at  the  Julius  Smelter  near  Goslar,  in  which  zinc  ores 
from  the  Rammelsberg  are  worked. 

"While  the  blendes  contain  indium  as  the  sulfide,"  continued 
Winkler,  "Hoppe-Seyler  found  it  in  another  form,  which  could  not 
be  definitely  determined,  in  a  tungsten  ore  from  an  unknown  locality, 
and  later  in  the  wolframite  from  Zinnwald.  The  latter  contains  0.0228 
per  cent  of  indium.  In  the  meantime,  I  have  placed  many  minerals 
(without  previous  concentration,  to  be  sure)  before  the  slit  of  the 
spectroscope,  but  have  never  found  one  which  gave  the  desired 
reaction.  It  therefore  seems  as  if  the  occurrence  of  indium  in  nature 
is  exceedingly  scarce  or  it  must  in  most  cases  play  the  role  of  a  diffi- 
cultly discoverable  satellite"  (81). 

In  1873  H.  B.  Cornwall  detected  indium  in  zinc  blendes  from  West 
Ossipee  and  Eaton,  New  Hampshire,  and  from  Roxbury,  Connecticut. 
The  last-mentioned  blende  was  so  rich  that  the  indium  line  showed 
distinctly  when  the  spectroscopic  test  was  applied  to  the  raw  powdered 
blende,  without  use  of  acids.  In  1876  he  found  that  certain  zinc 
blendes  from  Nevada  County,  Colorado,  also  were  rich  in  indium  (82, 
55).  In  the  following  year  A.  and  G.  de  Negri  of  the  University  of 
Genoa  found  that  the  calamine  from  the  Oneta  mine  in  the  province  of 
Bergamo,  Italy,  was  rich  in  this  element  (S3).  W.  N.  Hartley  and 
H.  Ramage  found  that  the  pumice  from  the  Krakatoa  eruption  of 
1883  contained  small  amounts  of  it  (84,  85).  Although  this  metal 
is  usually  associated  with  zinc  blende,  H.  Romeyn,  Jr.  found  an  indium 
content  of  from  1.0  to  2,8  per  cent  in  cross  sections  of  a  pegmatite  dike 
in  western  Utah,  which  contained,  among  other  minerals,  iolite  (cor- 
dierite,  magnesium  ferrous  aluminum  silicate)  in  which  part  of  the 
aluminum  had  probably  been  replaced  by  indium  (84,  86). 

Indium,  unlike  germanium,  is  found  in  zinc  blendes  which  are 
geologically  old.  Whereas  cadmium  occurs  mainly  in  the  well-formed 
crystals  of  pure  zinc  blende,  indium  is  found  in  the  fine-grained 
mixtures  in  thin  ramifying  cracks  (84).  Professor  Georges  Urbain 
found  that  blendes  rich  in  germanium  are  usually  rich  also  in  gallium 
put  poor  in  indium  (84,  87). 

Commercial  Development  of  Indium.  William  S.  Murray  and  his 
colleagues  searched  many  years  for  an  ore  containing  paying  quantities 
of  indium.  After  examining  in  vain  hundreds  of  specimens  of  zinc, 
lead,  silver,  and  gold  ores,  they  finally  found  one  that  gave  an  unusually 
intense  and  unwavering  blue  line  in  the  spectroscope.  The  source  of 
this  specimen  was  finally  traced,  and  a  deposit  of  35,000  tons  of  the 
ore  was  found  to  average  1.93  ounces  of  indium  per  ton.  In  1932  Mr. 
Murray  displayed  before  the  Rotary  Club  in  Utica,  New  York,  an 
indium  ingot  weighing  more  than  three  thousand  grams  (55). 


648  DISCOVERY  OF  THE  ELEMENTS 

Daniel  Gray  perfected  a  stable  bath  from  which  indium  can  be 
plated  simultaneously  with  other  elements  (90).  Alloyed  with  precious 
metals,  indium  has  been  made  into  jewelry,  alloyed  with  silver,  it  is 
sometimes  used  to  plate  silverware  with  a  suiface  resistant  to  tarnish; 
in  the  form  of  an  amalgam,  it  can  be  used  for  dental  fillings  ( 88,  89,  93 ) 

The  portraits  of  Reich  and  Richter  and  much  of  the  information 
about  indium  have  been  obtained  through  the  kind  assistance  of  Pro- 
fessor L.  W.  McCay  of  Princeton  University  and  Professor  O.  Brunck, 
Rectoi  of  the  Freiberg  Academy. 

LITERATURE  CITED 

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WiLhelm   Weicher,   Leipzig,   1905,   pp    4—7. 

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p    210. 

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182-6 

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(6)  Ibid.,  p.  23. 

(7)  OSTWALD,  WILHELM,  "Manner  der  Wissenschaft— R    W.  Bunsen/'  Ref.    (2) 

pp    13-22 

(8)  "Chemical   Society   Memorial   Lectures,    1893-1900,"    Gurney    and    Jackson. 

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pp.  25-30. 

(10)  VON    MEYER,    ERNST,    "History    of    Chemistry,"    3rd    English    edition    from 

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(11)  OSTWALD,  WILHELM,  "Manner  der  Wissenschaft-R,  W.  Bunsen,"  Ref.   (2), 

pp.  35-6. 

(12)  Ibid.,  p.   40 

(13)  "Chemical  Society  Memorial  Lectures,  1893-1900,"  Ref     (8),   p.  553. 

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MELVILLE,  "Edinburgh  Physical  and  Literary  Essays,  Edinburgh,  1752,  Vol. 
2,  p.  12, 

( 65 )  WINDERLICH,  RUDOLF,  "August  Wilhelm  von  Hofmann/'  Aus  der  Heimat,  55, 

49-53  (Apr.-May,  1942). 

(66)  GROTH,  P.  H.?  "Entwicklungsgeschichte  der  mineralogischen  Wissenschaften/' 

Juhus  Springer,  Berlin,  1926,  p.  251. 

(6/)     BREITHAUPT,  AUGUST,  "Neue  Minerale:     Mangano-Calcit  .  .  .  Kastor  und  Pol- 
lux," Fogg.  Ann.,  69  (1846). 

(68)  WESTERMANN,  ILJA,  "Aus  Plattners  Leben  und  Werken,"  Metall  und  Erzf  30, 

101-3  (March  2,  1933) 

(69)  WTJBZBACH,  C.  VON,  "Biographisches  Lexikon  des  Kaiserthums  Oesterreich," 

Vol  22,  K.  K  Hof-  und  Staatsdruckerei,  Vienna,  1856-91,  pp.  452^3  (article 
on  Poda  von  Neuhaus ) ,  Vol.  18,  pp  394-6  ( article  on  Mittrowsky,  Baron 
Joharm  Nepomuk);  Vol.  2,  pp.  71^t  (article  on  Born,  Ignaz  EcUer  von). 

(70)  BORN,  I.  E.  VON,  "Einige  mineralogische  Nachrichten/'  Crell's  Ann.,  16,  195-6 

(1791). 


SOME  SPECTROSCOPIC  DISCOVERIES  651 

( 71 )  KLAPROTH,  M.  H.,  "Analytical  Essays  towards  Promoting  the  Chemical  Knowl- 

edge of  Mineral  Substances,"  T.  Cadell  and  W  Davies,  London,  1801,  pp. 
238-47,  348-67,  471-5,  "Beytrag  zur  chemischen  Naturgeschichte  des 
Pflanzenalkali,"  Crell's  Ann,  27,  90-6  (1797).  Articles  on  leucite  and 
lepidolite. 

( 72)  BOTTGER,  R.  C.,  "Ueber  das  Vorkommen  von  Casium,  Rubidium,  und  Thallium 

in  der  Nauheimer  Soole,"  Ann  ,  127,  368-70  ( 1863 ) ;  128,  240-7  ( 1863 ) . 

(73)  BOTTGER,  R.   C.,  "Vorkommen  des  Thalliums,"  /.  prakt    Chem,  90,  478-9 

(1863). 

(74)  Obituaries   of  Grookes  and   of  Nordenskibld,   Minerdogical  Mag.,   18,   394 

(1916-19);  13,  191-2  (1901-3). 

(75)  NORDENSKIOLD,  A.  E  ,  "Die  Selenminerahen  von  Skrikemm,"  J.  prakt.  Chem., 

102,  456-8  (1867);  Oefvers.  af  Akad  Forhandl.  1866,  p  361. 

(76)  CARSTANJEN,  E,  "Ueber  das  Thallium  und  seine  Verbmdungen,"  J.  prakt 

Chem.,  102,  65-8  (1867). 

(77)  BHETTHAUPT,  AUGUST,  "Mineralogische  Studien,"  Arthur  Felix,  Leipzig,  1866, 

p.  93. 

(78)  WILLIS,  L.  G.,  "Bibliography  of  References  to  the  Literature  on  the  Minor 

Elements  and  Their  Relation  to  Plant  and  Animal  Nutrition,"  Chilean  Nitrate 
Educational  Bureau,  New  York,  1939,  columns  877-80. 

(79)  BOTTGER,  R.  C.,  "Extraction  of  indium  from  the  products  of  the  roasting  of 

blende,"  Chem    News,  15,  228  (May  3,  1867),  /    prakt.  Chem,  98,  26 
(1866). 
(50)     PETERSEN,  "Rudolph  Christian  Boettger,"  Ber ,  14,  2913-9  (1881). 

(81)  WTNKLER,  CLEMENS,  "Beitrage  zur  Kenntniss  des  Indiums/'  /.  prakt.  Chem., 

102,273-4  (1867). 

(82)  CORNWALL,  H.  B  ,  "Indium  in  American  blendes,"  Am.  Chemist,  3,  242  (Jan., 

1873);  7,339  (March,  1877). 

(S3)     NEGRI,  A  DE  and  G.  DE  NEGRI,  "Calamina  ncca  d'indio,"  Gazz.  chim.  ital.,  8, 
120  (1878). 

(84)  "Gmelin's  Handbuch  der  anorganischen  Chemie,"  8th  ed,  Vol.  36,  Verlag 

Chemie,  Berlin,  1936,  pp  1-8,  VoL  37,  pp.  1-6  History  and  occurrence  of 
gallium  and  indium. 

(85)  HARTLEY,  W.  N.,  and  H.  RAMAGE,  Proc.  Roij  Soc.  (London),  68,  99  (1901), 

(86)  ROMEYN,  H.,  "Indium  and  scandium  in  pegmatite,"  J.  Am.  Chem.  Soc.,  55, 

3899-3900  (Sept,  1933). 

(87)  URBAIN,  G.,  "Analyse  spectrographique  des  blendes,"  Compt.  rend.,  149,  602- 

3  (Oct.  11,  1909). 

(88)  LINFORD,  H.  B.,  "Indium,"  IruL  Eng.  Chem,  News  Ed.,  18,  624  (July  25, 

1940), 

( 89 )  LAWRENCE,  R.  E.,  and  L,  R.  WESTBROOK,  "Indium.    Occurrence,  recovery,  and 

uses,"  Ind.  Eng.  Chem.,  30,  611-4  (June,  1938) 

(90)  MURRAY,  W.  S.,  "Indium  available  in  commercial  quantities/*  Ind.  Eng.  Chem., 

24,  686  (June,  1932). 

(91 )  BUGGE,  G ,  "Der  Alchimist    Die  Geschichte  Leonhard  Thurneyssers— des  Gold- 

machers  von  Berlin,"  Wilhelm  Limpert  Verlag,  BerHn,  1939,  pp.  117—8. 

(92)  VOGEL,  OTTO,  "Thurneyssers  Flammenfarben  zur  Unterscheidung  der  Metalle/' 

Chem.-Ztg.,  38,  180  (1914). 

(93)  MURRAY,  W,  S.,  "Production  and  deposition  of  indium,"  Ind.  Eng.  Chem.3 

News  Ed.t  11,  300  (Oct.  20,  1933). 


TABLE  11. 
THE  ATOMIC   WEIGHTS   OP   THE   ELEMENTS 
JJistributton  of  the  Elements  in  Periods 

Groups 

Higher 

-ftlU 

forming 

Typical  or 
1st  small 
FLi-lod 

Large  Periods 

1st 

2nd 
lib    Bfl 

Bid 

4  til 

Mh 

I 

K,0 

Li   «=7 

K   39 

Cs  1^3 

— 

— 

II 

RO 

Le  -9 

Ca40 

b      87 

IiaI37 

— 

— 

III 

RA 

B    =11 

Sc  44 

Y     tt9 

La  L38 

YblTd 

— 

IV 

RO, 

C_    T  O 
P1  L-& 

Tl  48 

Zr    90 

Ce  140 

— 

Th232 

V 

RA 

N    =14 

V   61 

Kb  94 

— 

Tal82 

— 

VI 

RO, 

0    =16 

Cr52 

Mo  9G 

— 

W  184 

ijr240 

VII 

RA 

F    i=10 

Mn55 

— 

— 

— 

— 

/ 

KB  56 

BulOd 

— 

Os  101 

— 

VIII 

• 

Co  585 

Eh  104 

— 

Ir  193 

— 

I 

Hi  50 

IM106 

— 

Pt  196 

— 

I 

HP 

El-1  Na»23 

Cu  63 

Atf  lt»b 

— 

AulOS 

— 

II 

XO 

MC  =5  —  1 

Zn  G5 

CdlU 

— 

Hg2UO 

— 

III 

HA 

Al  ~27 

G&70 

In  113 

— 

Tl  204 

— 

IV 

R03 

Si    =28 

Ge72 

bn  llfl 

— 

TbUUG 

— 

V. 

HA 

P    =31 

As  76 

fab  120 

— 

Bi  208 

— 

VI. 

RO, 

S    -32 

Se  79 

Te  12S 

— 

— 

— 

VII. 

HA 

Cl   =355 

Bi  80 

I     127 

— 

— 

— 

2nd  small 
Period 

let 

2nd 

3rd 

4th 

6th 

I  ti£r  Ponn<Ts 

From  Mendeleev's  "Principles  of  Chemistry,"  Vol.  1 
Mendeleev's  Periodic  Table  of  the  Elements.     Tlie 

groups  are  arranged  horizontally  instead  of  vertically. 


Refrain  from  illusions,  insist  on  work  and  not  words, 
patiently  search  divine  and  scientific  truth  (1,  15) 

Wer  ruft  das  Einzelne  zur  allgemeinen  Weihe, 
Wo  es  in  herrlichen  Accorden  schlagt?  (2)** 

*  Who  calls  the  individual  to  the  universal  consecration,  where  it  vibrates  in  glorious 
harmony? 


24 

Periodic  system  of  the  elements 


Before  continuing  the  story  of  the  discouenj  of  the  chemical 
elements,  it  will  be  necessary  to  outline  the  early  attempts  at 
classification  made  by  Dobereiner,  Begmjer  de  Chancourtois,  and 
Newlands,  and  to  discuss  briefly  the  periodic  system  of  the  ele- 
ments which  was  developed  independently  by  Lothar  Meyer  and 
Mendeleev.  This  classification  enabled  Mendeleev  to  predict  the 
properties  of  a  number  of  undiscovered  elements  and  of  their 
compounds  with  surprising  accuracy,  and  proved  to  be  of  great 
assistance  in  all  subsequent  discoveries  of  new  elements. 


A 


.Ithough  the  alkali  metals  and  the  spectroscope  aided  greatly 
in  revealing  hidden  elements,  each  new  discovery  was  an  unexpected 
event.  Before  the  periodic  law  was  discovered  independently  by  Lothar 
Meyer  and  by  D.  I.  Mendeleev  in  1869,  there  was  no  way  to  predict  what 
elements  lay  undiscovered  nor  to  foretell  their  physical  and  chemical 
properties. 

One  of  the  important  steps  leading  up  to  this  great  generalization  was 
the  discovery  by  Professor  Johann  Wolfgang  Dobereiner  of  Jena  of  his 
famous  triads  (10,  11).  He  was  born  in  December,  1780,  the  son  of  a 
coachman  at  Hof ,  near  Bayreuth.  On  a  foundation  of  only  meager  elemen- 
tary instruction,  practical  training  in  various  pharmacies,  and  attendance 
at  a  few  lectures  on  philosophy,  chemistry,  botany,  mineralogy,  and 
languages,  he  developed  such  great  ability  for  original  research  in  chem- 
istry that  in  1810  A.  F.  Gehlen,  the  editor,  and  Duke  Carl  August  made 
him  professor  extraordinary  of  chemistry  at  Jena  (22).  His  personal  and 
intellectual  qualities  soon  won  the  high  esteem  of  the  Duke  and  the  poet 
Goethe  (23,  24,27,44). 

Dobereiner  noticed  in  1829  that  there  are  several  triads  in  which  the 
middle  element,  that  is,  the  one  whose  atomic  weight  lies  midway  between 
those  of  the  other  two,  has  properties  which  likewise  are  a  mean  of  those 
of  the  other  elements  of  the  triad  (29,  31). 

Professor  Dobereiner  also  made  a  thorough  investigation  of  the 

653 


654 


DISCOVERY  OF  THE  ELEMENTS 


Johann     Wolfgang     Dobereiner,      1780- 

1849.  Professor  of  chemistry  at  Jena,  His 
discovery  of  the  triads  was  an  important 
step  toward  the  systematic  classification  of 
the  chemical  elements  He  wrote  many 
books  and  papers  on  general  and  pharma- 
ceutical chemistry,  mineral  waters,  the 
manufacture  of  vinegar,  and  the  use  of 
platinum  as  a  catalyst.  The  original  of 
this  portrait  is  in  the  City  Museum  at  Jena. 


From  Chemmttus'  "Die  Chemie  in  Jena  von 

Rolfinck  bis  Knorr"* 


catalytic  action  of  platinum^  and  wrote  books  on  general  and  pharma- 
ceutical chemistry,  on  the  manufacture  of  vinegar,  and  on  mineral  waters 
for  therapeutic  purposes.  Even  before  the  time  of  Liebig,  he  gave 
practical  laboratory  instruction  in  analytical  chemistry.  He  died  on 
March  24,  1849. 

Alexandra  E.  Beguyer  de  Chancourtois  (1820-1886),  a  professor  of 
geology  in  the  School  of  Mines  in  Paris,  made  in  1862  a  "telluric  screw," 
or  helix,  on  a  vertical  cylinder,  on  which  he  placed  the  symbols  of  the 
elements  at  heights  proportional  to  their  atomic  weights.  He  plotted  the 
atomic  weights  as  ordinates  on  the  generatrix  of  a  cylinder  the  circum- 
ference of  which,  since  the  atomic  weight  of  oxygen  is  16,  he  divided 
into  sixteen  equal  parts.  He  then  traced  on  the  surface  of  the  cylinder 
a  helix  making  a  45°  angle  with  the  axis.  The  spiral  therefore  crossed 
a  given  generatrix  at  distances  from  the  base  which  were  a  multiple  of 
16  Thus  lithium,  sodium,  and  potassium,  with  atomic  weights  of  7,  23, 
and  39,  respectively,  fell  on  one  perpendicular,  whereas  oxygen,  sulfur, 
selenium,  and  tellurium  fell  on  another. 

Beguyer  de  Chancourtois  observed  the  great  similarity  existing 
between  elements  appearing  on  the  same  generatrix,  mentioned  the 
periodic  recurrence  of  properties,  and  stated  that  "the  properties  of 
substances  are  the  properties  of  numbers."  He  presented  to  the  French 

*  Reproduced  by  courtesy  of  Dr.  Fritz  Chernnitius. 

t  Dobereiner  was  assisted  for  a  time  by  Gottfried  Wilhelm  Osann,  whose  researches 

on  platinum  led  to  the  discovery  of  ruthenium  by  Klaus. 


PERIODIC  SYSTEM  OF  THE  EIJEMENTS         655 


A  Portion  of  the 
Telluric  Screw  of 
Beguyer  de  Chancourtois 


656 


DISCOVERY  OF  THE  ELEMENTS 


Academy  a  lithograph  and  a  model  of  his  "telluric  screw"  (12,  13,  14). 
Unfortunately,  his  heavy,  obscure  literary  style,  his  use  of  terms  more 
familiar  to  geologists  than  to  chemists,  and  the  failure  of  the  Comptes 
rendas  to  publish  a  reproduction  of  his  diagram  all  contributed  to  a  lack 
of  appreciation  of  his  contribution*  (19)- 

Another  important  advance  in  the  classification  of  the  elements  was 
made  by  John  Alexander  Reina  Newlands.  He  was  born  in  Southwark, 
England,  in  1837,  and  was  educated  privately  by  his  father,  a  minister  of 


Alexandre-Emile      Beguyer      de      Chan- 

courtois,  1820-1886.  Inspector-general 
of  mines  and  professor  of  geology  at  the 
ficole  Supe"neure  des  Mines  an  Paris  He 
made  geological  explorations  in  France, 
Asia  Minor,  Iceland,  and  Greenland.  As 
a  humanitarian  reform  to  prevent  acci- 
dents from  firedamp,  lie  compelled  mine 
owners  to  sink  two  shafts  for  each  coal 
His  most  important  contribution 


mine 


to  chemistry  was  Ins  spiral  periodic 
arrangement  of  the  elements  Courtesy 
Mme.  Jean  Presne  and  the  Ecole 
Sup6neure  des  Mines,  Pans 


the  Established  Church  of  Scotland.  When  J.  A.  R.  Newlands  was  nine- 
teen years  old  he  entered  the  Royal  College  of  Chemistry  to  study  under 
A,  W.  von  Hofmann,  His  sympathy  for  Italy,  the  land  of  his  maternal 
ancestors,  led  him  to  volunteer  in  1860  for  military  service  under  Giuseppe 
Garibaldi.  When  Italian  freedom  had  been  won  he  returned  to  London, 
practiced  for  a  time  as  an  analytical  chemist,  and  taught  at  the  Grammar 
School  of  St.  Saviour  s,  Southwark,  at  the  School  of  Medicine  for  Women, 
and  at  tihe  City  of  London  College.  For  many  years  he  was  the  chief 
chemist  in  a  large  sugar  refinery  at  Victoria  Docks,  and  with  his  brother, 
Mr.  B.  E,  R.  Newlands,  he  afterward  published  a  treatise  on  sugar. 

In  1864  he  arranged  the  elements  in  the  order  of  increasing  atomic 
weights,  and  noticed  that  after  each  interval  of  eight  elements,  similar 


9  The  Comptes  rendus  finally  published  it,  however,  nearly  thirty  years  later 
ref.  (35). 


See 


PERIODIC  SYSTEM  OP  THE  ELEMENTS 


657 


physical  and  chemical  properties  reappeared  ( 16 )  Thus  he  divided  them 
into  natural  families  and  periods,  but  for  this  law  of  octaves  he  gained 
nothing  but  public  ridicule  from  the  English  Chemical  Society.  So  little 
was  the  importance  of  atomic  weights  realized  that  a  certain  wag  once 
asked  him  if  he  could  not  get  the  same  result  by  arranging  the  elements 
according  to  the  initials  of  their  names  (3,  18).  The  Chemical  Society 
refused  to  publish  his  paper,  but  in  1887  the  Royal  Society  awarded  him 
the  Davy  Medal  for  it  (9,  17,  42). 


John  Alexander  Reina  Newlands,** 
1837-1898.  Professor  of  chemistry  at 
the  School  of  Medicine  for  Women 
and  at  the  City  of  London  College 
Discoverer  of  the  law  of  octaves.  He 
was  an  authority  on  the  chemistry  of 
sugar  refining. 


In  a  biographical  sketch  in  Nature,  W.  A.  T.  (Tilden?)  stated  that 
this  tardy  recognition,  which  came  five  years  after  the  same  honor  had 
been  conferred  on  Mendeleev  and  Lothar  Meyer,  did  not  do  Newlands 
full  justice.  "If  Newlands  had  been  a  Frenchman/'  said  he,  "the  Academy 
of  Sciences  and  the  Chemical  Society,  even  if  they  had  at  first  fallen  into 
error,  would  have  taken  care  that  in  the  distribution  of  honours  their 
own  countryman  should  not  come  in  last"  (36).  Nevertheless,  Newlands 
kept  up  his  regular  attendance  at  the  meetings  of  the  Chemical  Society 
and  won  many  friends  by  his  kindness  and  courtesy.  He  died  of  influenza 
on  July  29,  1898. 

The  periodic  system  of  the  elements  was  developed  independently  and 
almost  simultaneously  by  Lothar  Meyer  in  Germany  and  D.  I.  Mendeleev 
in  Russia,  Julius  Lothar  Meyer  was  born  on  August  19,  1830,  at  Varel  on 

*  This  portrait  was  obtained  through  the  courtesy  of  Mr.  R.  B   Pilcher,  Registrar  and 
Secretary  of  the  Institute  of  Chemistry  of  Great  Britain  and  Ireland. 


658 


DISCOVERY  OF  THE  ELEMENTS 


the  Jade  in  the  Grand  Duchy  of  Oldenburg.  His  father  was  a  physician, 
and  his  mother  used  to  assist  at  operations.  Both  of  the  sons  received  a 
medical  education,  but  Lothar  became  a  chemist  and  Oskar  Emil  a 
physicist.  Since  Lothar  was  not  a  robust  child,  he  was  given  an  out-of- 
door  education  under  the  guidance  of  the  chief  gardener  at  the  Grand 
Duke  of  Oldenburg's  summer  palace  at  Rastede.  By  this  means  he 
developed  not  only  a  sturdy  body,  but  also  an  abiding  interest  in  Nature. 
He  received  his  degree  of  doctor  of  medicine  from  Wurzburg  University 

in  1854  (33). 

Meyer  knew  by  this  time  that  he  was  more  interested  in  research 
than  in  the  practice  of  medicine.    Therefore,  he  went  to  Heidelberg  to 


(Julius)  Lothar  Meyer,  1830-1895.  Ger- 
man chemist  and  physician.  Professor  of 
chemistry  at  Breslau  and  at  Tubingen. 
Co-discoverer  with  Mendeleev  of  the 
periodic  system  of  the  elements.  Some 
of  his  researches  were  on  the  gases  of  the 
blood,  the  molecular  volumes  of  chemical 
compounds,  atomic  weights,  a  sensitive 
thermo-regulator,  the  paraffins,  and  the 
constitution  of  fuchsrn. 


study  under  Robert  Bunsen  and  G.  R.  Kirchhoff,  where  the  latter  soon 
aroused  in  him  an  intense  interest  in  applied  mathematics.  In  1858  Lothar 
Meyer  became  a  privatdocent  in  physics  and  chemistry  at  Breslau,  and 
six  years  later  his  brother  Oskar  Emil  joined  him  there  as  professor  of 
mathematics  and  mathematical  physics,  Lothar  Meyer's  book,  "Moderne 
Theorien  der  Chemie/'  which  was  published  in  the  same  year  and  which 
contained  his  first  incomplete  periodic  table,  made  his  name  well  known 
throughout  the  scientific  world  (4). 

In  1868  he  went  to  the  Carlsruhe  Polytechnicum,  which,  during  the 
war  between  France  and  Germany,  was  used  as  an  army  hospital.  Here 
he  made  good  use  of  his  medical  training.,  and  rendered  such  valuable 


PERIODIC  SYSTEM:  OF  THE 


659 


:::'::-:  •  r  T   :!;•:;:;'•  :^ 


;-L  ',  i  *  i'i '.  'i  3     "  •  -  '  -  <  - "  J ."  i !  *  l-i*  *  I 


CD 
OS 
en 

.S3 

CJ 

CO 

•g 

CO 

cc 


•a 


O 
-P—  i 

s 

o 

•a 


ft) 


o 

•  •""1 

I 


o 


o 

"S 


WJ 


660 


DISCOVERY  OF  THE  ELEMENTS 


service  as  army  surgeon  that,  at  the  close  of  the  war,  he  was  awarded  a 

medal  (4). 

In  December,  1869,  he  arranged  fifty-six  elements  in  a  table  con- 
sisting of  groups  and  sub-groups  (28,  30).  He  also  drew  a  curve  showing 
the  relation  between  the  atomic  weights  and  the  atomic  volumes  of  the 
elements,  and  found  that  this  is  divided  by  maxima  into  six  sections.  In 


J.  Heyrovsky,  Collection  Cxechoslov.  Chem.  Communications 
Dmitri  Mendeleev  and  Bohuslav  Brauner  in  Prague,  1900. 
The  latter  was  a  professor  of  chemistry  at  the  Bohemian 
University  of  Prague.  He  wrote  a  charming  biographical 
sketch  of  his  friend,  Mendeleev,  who  once  had  the  portraits 
of  Lecoq  de  Boisbaudran,  Nilson,  Winkler,  and  Brauner 
framed  together  because  they  had  contributed  most  toward 

the  development  of  his  periodic  system  (40). 


the  second  and  third  sections  the  atomic  weight  increases  by  increments 
of  sixteen  units,  but  in  the  fourth  and  fifth  sections  the  atomic  weight 
increments  are  much  larger—about  forty-six  units  each.  He  then  pre- 
pared other  curves  which  showed  that  fusibility,  volatility,  malleability, 
brittleness,  and  electrochemical  behavior  are  also  periodic  properties.  The 
volatile  and  easily  fusible  elements  lie  on  the  ascending  portions  of  the 


PERIODIC  SYSTEM  OF  THE  ELEMENTS  661 

curves,  whereas  the  refractory  elements  are  on  the  descending  portions  or 
at  the  minima. 

In  1876  Lothar  Meyer  became  a  professor  of  chemistry  at  the  Uni- 
versity of  Tubingen.  He  served  the  university  devotedly  in  this  capacity 
and  as  rector,  and  his  fame  and  ability  attracted  students  from  all  parts  of 
the  world  (4).  He  died  on  April  11,  1895. 

Dmitri  Ivanovich  Mendeleev  was  born  in  Tobolsk  in  western  Siberia 
on  February  8,  1834.  He  was  of  Russian  and  Mongolian  descent,  and 
was  the  youngest  child  in  a  very  large  family.  Some  biographers  mention 
seventeen  children,  but  Mendeleev's  personal  friend  Dr.  Bohuslav  Brauner 
stated  that  there  were  fourteen  (37). 

Maria  Kornileva  Mendeleeva  was  especially  fond  of  her  youngest 
child,  Dmitri,  and  called  him  by  the  affectionate  name,  Mitjenka  (15). 
While  Mitjenka  was  still  very  young,  his  father,  who  was  the  director  of 
the  Tobolsk  gymnasium,  lost  his  sight  because  of  cataracts  in  both  eyes. 
Although  the  government  granted  him  a  pension  of  one  thousand  roubles 
(about  $500),  this  would  not  begin  to  feed  and  clothe  his  large  family. 
It  therefore  fell  to  the  lot  of  Maria  Mendeleeva  not  only  to  care  for  her 
poor,  blind  husband  and  her  eight  children  who  were  still  dependent,  but 
also  to  undertake  a  business  career.  The  Kornilev  family  had  founded 
the  first  glassworks  and  paper  mill  in  Tobolsk,  and  Maria  Mendeleeva  now 
established  in  the  neighboring  village  of  Axemziansk  her  own  glassworks, 
which  she  directed  as  an  efficient  and  successful  executive  while  carrying 
her  heavy  household  burdens  (9,  21,  37). 

As  a  child,  Dmitri  excelled  in  mathematics,  physics,  and  history,  but 
he  never  liked  Latin.  His  first  science  teacher  was  his  brother-in-law, 
Bassargin,  a  well-educated  Russian  who  had  been  exiled  for  attempting 
to  start  a  revolution  (9,  25).  Bassargin  was  one  of  the  "Decembrists" 
who  in  December,  1825,  made  an  unsuccessful  attempt  to  overthrow  the 
Emperor  Nicholas  I. 

Dmitri  completed  the  gymnasium  course  at  the  age  of  sixteen  years, 
but  shortly  before  his  -graduation  a  profound  double  tragedy  had  occurred. 
His  helpless  father  had  died  of  tuberculosis,  and  the  glassworks  had 
burned  to  the  ground.  Maria  Mendeleeva,  then  fifty-seven  years  old, 
secured  horses  and  started  out  with  her  two  youngest  children  for  Moscow, 
hundreds  of  miles  away.  Unable  to  enroll  Dmitri  in  the  university  be- 
cause of  insufficient  political  influence,  she  went  to  Petrograd  to  interview 
Pletnov,  the  director  of  the  Central  Pedagogic  Institute  and  friend  of  her 
late  husband,  who  succeeded  in  obtaining  financial  aid  from  the  govern- 
ment and  in  making  it  possible  for  Dmitri  to  begin  his  work  in  the  de- 
partment of  physics  and  mathematics  (34). 

A  few  months  later  Maria  Mendeleeva  laid  down  her  heavy  burdens, 


662  DISCOVERY  OF  THE  ELEMENTS 

consoled  in  her  last  hours  by  the  thought  that  her  Dmitri  was,  after  all, 
to  have  an  education,  Some  years  later  he  wrote  in  the  preface  to  his 
famous  book  on  solutions: 

This  investigation  is  dedicated  to  the  memory  o£  a  mother  by  her  youngest 
offspring.  Conducting  a  factory,  she  could  educate  him  only  by  her  own  work. 
She  instructed  by  example,  corrected  with  love,  and  in  order  to  devote  him  to 
science  she  left  Siberia  with  him,  spending  'thus  her  last  resources  and  strength. 
When  dying,  she  said,  "Refrain  from  illusions,  insist  on  work,  and  not  on  words. 
Patiently  search  divine  and  scientific  truth,"  She  understood  how  often  dia- 
lectical methods  deceive,  how  much  there  is  stiU  to  be  learned,  and  how,  with 
the  aid  of  science  without  violence,  with  love  but  firmness,  all  superstition,  un- 
truth, and  error  are  removed,  bringing  in  their  stead  the  safety  of  discovered 
truth,  freedom  for  further  development,  general  welfare,  and  inward  happiness. 
Dmitri  Mendeleev  regaids  as  sacred  a  mother's  dying  words.  October,  1887 

(I). 


Henri-Victor  Regnault,  1810-1878.  French 
chemist  and  physicist  He  made  precise 
measurements  of  specific  heats  and  heats 
of  fusion  and  vaporization,  and  of  the 
velocity  of  sound,  and  contributed  to  the 
theory  of  organic  radicals.  Among  his 
students  may  be  mentioned  Canmzzaro, 
Kekul£,  and  Mendeleev. 


When  Mendeleev  graduated  from  the  Pedagogical  Institute,  he 
received  a  gold  medal  for  excellence  in  scholarship,  Between  1859  and 
1861  he  worked  with  H.-V.  Regnault  in  Paris  and  with  Robert  Bunsen 
in  Heidelberg.  Upon  returning  to  Petrograd  in  1861,  he  was  granted  his 
doctorate  and  was  appointed  professor  of  chemistry  at  the  Technological 
Institute.  Eight  years  later  he  became  the  professor  of  general  chemistry 
at  the  University  of  Petrograd. 


PERIODIC  SYSTEM  OF  THE  ELEMENTS  663 

In  March  of  the  same  year  he  presented  to  the  Russian  Chemical 
Society  his  famous  paper  on  "The  relation  of  the  properties  to  the  atomic 
weights  of  the  elements."  Mendeleev's  great  merit  as  a  discoverer  lay 
in  the  boldness  with  which  he  asserted  that  the  atomic  weights  of  certain 
elements  which  did  not  fit  into  his  system  had  been  incorrectly  deter- 
mined, and  that  new  elements  would  some  day  be  discovered  to  fit  into 
the  vacant  spaces  in  the  periodic  table  (30,  32).  He  even  predicted  the 
properties  of  a  number  of  these  undiscovered  elements,  and  three  of 
them,  which  he  called  ekasilicon,  ekaboron,  and  ekaaluminum,  were  dis- 
covered during  his  lifetime,  and  are  now  known,  respectively,  as  ger- 
manium, scandium,  and  gallium.*  Thus  he  was  able  to  say  in  his  Faraday 
lecture  in  1889:  "The  law  of  periodicity  first  enabled  us  to  perceive 
undiscovered  elements  at  a  distance  which  formerly  was  inaccessible  to 
chemical  vision;  and  long  ere  they  were  discovered,  new  elements  ap- 
peared before  our  eyes  possessed  of  a  number  of  well-defined  properties" 
(5?  20,  28).  Mendeleev's  periodic  table  (6)  was  more  complete  than  any 
of  the  preceding  ones,  and  more  thoroughly  founded  on  experiment. 

He  willingly  recognized  Lothar  Meyer's  claim  to  independent  dis- 
covery. He  was  asked  to  speak  before  the  British  Association  in  Man- 
chester in  1887,  but,  feeling  unable  to  address  the  assembly  in  English, 
he  simply  rose  and  bowed,  Lothar  Meyer  then  rose  to  thank  the  English 
scientists  for  their  hospitality  and,  fearing  lest  a  wrong  impression  be 
made,  began  with  the  modest  words,  "I  am  not  Mendeleev.  I  am  Lothar 
Meyer."  He  also  was  greeted  with  generous  applause.  In  1882  the  Davy 
Medal  had  been  awarded  jointly  to  Mendeleev  and  Meyer  (7). 

Professor  William  McPherson,  president  of  the  American  Chemical 
Society  in  1930,  said  in  his  presidential  address  that  he  once  asked  a  for- 
mer student  who  had  distinguished  himself  in  the  field  of  literature 
whether  he  had  derived  any  benefit  from  his  course  in  chemistry.  The 
young  gentleman  replied  that  the  idea  that  had  helped  most  to  frame 
his  philosophy  of  Me  was  the  periodic  law.  "He  had  been  much  con- 
fused by  what  seemed  to  him  an  entire  absence  of  order  in  the  universe; 
.  .  .  and  he  recognized  for  the  first  time  in  his  study  of  the  periodic  law 
unmistakable  evidence  of  order  in  the  universe,  for  in  no  other  kind  of 
universe  could  one  predict  not  only  the  existence  of  unknown  elements 
but  the  properties  of  these  unknown  elements  as  well .  .  ."  (45). 

Mendeleev  and  his  students  contributed  to  all  branches  of  chemistry, 
and  his  literary  work  was  also  of  great  value.  His  textbook  "Principles  of 
Chemistry"  was  the  best  chemistry  text  in  the  Russian  language,  and  for 
this  reason  the  Petrograd  Academy  awarded  him  the  Demidoff  prize  (46). 
It  is  written  in  a  peculiar  style,  with  the  footnotes  occupying  more  space 

*  See  Chapter  25,  pp.  671-93. 


664 


DISCOVERY  OF  THE  ELEMENTS 


than  the  portion  of  the  text  in  large  type;  yet,  in  spite  of  its  strange  ap- 
pearance, it  is  a  great  chemical  classic.  He  also  investigated  the  Baku 
oil  fields,  the  naphtha  springs  in  the  Caucasus,  and  the  Pennsylvania  oil 
fields  (8,38). 


Courtesy  of  the  College  of  Charleston 

Lewis  Reeve  Gibbes,  1&10-1894.  Professor  of  chemistry 
and  other  sciences  at  the  College  of  Charleston.  He 
published  many  scholarly  papers  on  chemistry,  astronomy, 

zoology,  and  geology. 


Mendeleev  had  a  keen  appreciation  of  art  and  literature.  He  some- 
times wrote  articles  on  art,  and  his  study  was  furnished  with  pencil 
sketches  of  Lavoisier,  Newton,  Descartes,  Galileo,  Copernicus,  Graham, 
Mitscherlichj  Rose,  Chevreul,  Faraday,  Dumas,  and  Berthelot  drawn  by 
his  wife.  His  favorite  author  was  Jules  Verne,  and  his  chief  consolation 


PERIODIC  SYSTEM  OF  THE  ELEMENTS 


665 


during  his  last  illness  was  the  reading  of  "The  Journey  to  the  North  Pole" 
(9,  25).  He  died  of  pneumonia  on  Saturday,  February  2,  1907,  and  in 
a  telegram  to  the  widow,  Czar  Nicholas  said,  "In  the  person  of  Professor 
Mendeleev,  Russia  has  lost  one  of  her  best  sons,  who  will  ever  remain  in 
our  memory"  (5). 

In  1934,  in  honor  of  the  centenary  of  Mendeleev's  birth,  the  U.S.S.R. 
issued  a  set  of  four  denominations  of  commemorative  postage  stamps  bear- 
ing a  handsome  portrait  against  a  background  of  the  periodic  table. 
Reproductions  of  two  of  these  stamps  appeared  in  the  Journal  of  Chemical 
Education  in  July  of  that  year. 


TABIJ3  OF  CHEMICAL  ELEMENTS. 

a 

—4 
-3 
-2 
-1 
0 
4-1 
+2 
+3 

A 

Li=7 
Gl=9  3 
-B=ll 

B 

c 

c 
D 

5ERI 

E 

ES. 

F 

G 

H.I 

K 

GEOUPS. 

C=12 
N=14 
O=16 
F=19 

Na=23 

Mg=24 

81  =  28 
P=31 
S=32 
01=355 

K=39 
C&=40 

Ti=50 
V=513 
Cr=52.5 

Zn=65 

As=75 
Se=79 
Br=80 

Rt=85 
Sr=87.5 

Cb=94 
Mo=9G 

Aff=108 
Cd=112 

Sn=118 
Sb=122 
Te=128 
1=127 

Cs=133 
Ba=137 

Ta=182 
\V=184 

An  =  10G6 
Os=199 

11=204 
Pb=207 
Bi=2lO 

hdicon  Gr 
PLoephorua  Gt. 
Sulphur  Gr 
Chlonne  Gr 

Knlmm  Gr. 
Calcium  Gr. 

Al      97  c            /"v_..  co  c 

"Vfi-i      «^  •  P«      KR  •    fs\      ^Q  *  X?      KO  -   Pn      R3  fi           TT  —  12fl 

Iron  Gr. 
Platinum  Gr, 

Y=61.7 
In=74 

Zr=S9.5;Ce=92  ;  I*=92  ;  D=96           Er=112  ;  Th=115.7 
Ha=104;Eo=104,Pd=106  Pt=197;  Ir=197 

H=l                  Hg=200 

Courtesy  Wendell  H.  Taylor 


Gibbes's  Synoptical  Table  (1875) 


Another  very  early  classification  of  the  elements  was  made  by  Lewis 
Reeve  Gibbes,  professor  of  chemistry  at  the  College  of  Charleston,  South 
Carolina,  who  worked  out  the  first  version  of  his  "Synoptical  Table  of 
the  Chemical  Elements"  between  1870  and  1874,  and  in  1875  discussed 
an  improved  form  of  it  before  the  Elliott  Society  of  Charleston.  The 
hardships  of  the  reconstruction  period,  however,  made  prompt  publica- 
tion impossible.  When  tie  paper  was  finally  published  in  1886,  it  at- 
tracted little  attention  because  the  periodic  tables  of  Lothar  Meyer  and 
Mendeleev  were  already  well  known  (39). 

Instead  of  arranging  all  the  elements  in  the  order  of  increasing  atomic 
weights,  as  the  European  scientists  had  attempted  to  do,  Gibbes  (prob- 
ably without  knowledge  of  their  work)  conceived  the  idea  of  assembling 
the  well-known  families  on  horizontal  lines  numbered  from  minus  four 
to  plus  three  to  correspond  with  the  principal  valence  of  the  elements  in 
each  family.  In  each  of  these  horizontal  rows^  however,  he  placed  the 
elements  in  the  order  of  increasing  atomic  weights.  He  then  found  that 


666  DISCOVERY  OF  THE  ELEMENTS 

throughout  this  table,  which  he  had  based  on  stepwise  change  of  valence, 
most  of  the  elements  in  the  veitical  rows  also  followed  one  another  in  the 
order  of  increasing  atomic  weights.  Thus  his  approach  to  the  problem  of 
classifying  the  elements  was  the  reverse  of  that  used  by  Lothar  Meyer 
and  Mendeleev. 


Courtesy  Wendell  H.  Taylor 

Gibbes's  Diagram  (1875) 


Gibbes  observed  certain  blank  spaces  in  his  table  and  recognized  the 
possibility  that  these  might  some  day  be  filled  by  newly  discovered 
elements.  He  differentiated  the  two  subgroups  of  each  family  of  elements 
and  recognized  the  peculiarities  of  the  "typical  elements"  or  "group  intro- 


PERIODIC  SYSTEM  OF  THE  ELEMENTS  667 

ducers/'  carbon,  nitrogen,  oxygen,  and  fluorine.  He  also  constructed  a 
spiral  chart  based  on  his  "Synoptical  Table,"  Although  it  resembled 
somewhat  the  earlier  table  of  Beguyer  de  Chancourtois,  it  was  doubtless 
an  independent  discovery.  A  much  more  detailed  account  of  the  lif  e  and 
work  of  Professor  Gibbes  is  to  be  found  in  an  article  by  Wendell  H. 
Taylor  in  the  Journal  of  Chemical  Education  for  September,  1941  (39). 

LITERATURE  CITED 

(1)  HARROW,  B.,  "Eminent  Chemists  of  Our  Time,"  D.  Van  Nostrand  Co.,  New 

York  City,  1920,  p.  22,  P.  WALDEN,  "Dmitri  Iwanowitsch  Mendelejeff/'  Ber , 
41,  4723  ( 1908),    Last  words  of  Maria  Mendeleeva  to  her  son,  Dmitri 

(2)  VON  GOETHE,  J.  W.,  "Faust,"  part  1,  lines  148-9. 

(3)  VON  MEYER,  ERNST,  "History  of  Chemistry,"  3rd  English  edition  from  3rd 

German  edition,  The  Macmillan  Co  ,  London,  1906,  pp.  387-8. 

(4)  "Chemical  Society  Memorial  Lectures,  1893-1900,"  Gurney  and  Jackson,  Lon- 

don, 1901,  pp.  1427-9.    Lothar  Meyer  Memorial  Lecture  by  BEDSON. 

(5)  GRIFFITHS,  A.  B.,  "Biographies  of  Scientific  Men,"  Robert  Sutton,  London,  1912, 

pp.  126-36. 

(6)  MENDELEEV,  D,  "Principles  of  Chemistry,"  Vol.  2,  English  translation  from 

5th  Russian  edition  by  Kamensky  and  Greenaway,  Longmans,  Green  and  Co  9 
London,  1891,  p.  487. 

(7)  "Chemical  Society  Memorial  Lectures,  1893-1900,"  ref    (4),  p.  1420. 

(8)  THORPE,  T.  E.,  "Essays  m  Historical  Chemistry/'  The  Macmillan  Co  ,  London, 

1894,  p.  364. 

(9)  HARROW,  B,,  "Eminent  Chemists  of  Our  Time,"  ref   ( 1 ),  pp   19-40. 

(10)  VENABLE,  F.  P.,  "The  Development  of  the  Periodic  Law/'  Chem.  Publishing 

Co  ,  Easton,  Pa ,  1896,  pp.  11-12;  28-36. 

( 11 )  WURZER,  "Report  on  Dobereiner's  triads/'  Gilbert's  Ann.,  56,  332  ( 1816) ;  J  W 

DOBEREINER,  ibid.,  57,  436  (1817);  "Versuch  zu  einer  Gruppierung  der 
elementaren  Stoffe  nach  ihrer  Analogic,"  Pogg.  Ann.,  15,  301  ( 1829). 

(12)  BEGUYER  DE  CHANCOURTOIS,  A.-E.,  "Memoire  sur  un  classement  naturel  des 

corps  simples  ou  radicaux  appele  vis  tellurique/'  Compt.  Tend.,  543  757-61 
(Apr.  7,  1862);  840-3  (Apr.  21,  1862),  967-71  (May  5,  1862). 

(13)  VENABLE,  F,  P.,  "The  Development  of  the  Periodic  Law,"  ref.  (10),  pp.  73-6, 

82-5. 

(14)  BEGUYER  DE  CHANCOURTOIS,  A -E.,  "Tableau  du  classement  naturel  des  corps 

simples,  dit  vis  tellurique,"  Compt.  rend,  55,  600-1  (Oct   13,  1862). 

(15)  WALDEN,  P.,  "Dmitri  Iwanowitsch  Mendelejeff,"  Ber.,  41,  4719-4SOO  (1908), 

(16)  NEWLANDS,  J,  A.  R  ,  "On  relations  among  the  equivalents/'  Chem    NCIGS,  7, 

70-2  (Feb.  7,  1863);  10,  59-60  (July  30,  1864);  94-5  (Aug  20,  1864); 
"On  the  law  of  octaves,"  ibid,  12,  83  (Aug.  18,  1865),  "On  the  discovery 
of  the  periodic  law,  and  on  relations  among  the  atomic  weights,"  {bid,,  49, 
198-200  (May  2,  1884). 

(17)  Presentation  of  Medals,  Proc.  Rotj.  Soc.  (London),  43,  195  (Nov.  30,  1887). 

(18)  VENAELE,  F.  P.,  "The  Development  of  the  Periodic  Law/'  ref  ( 10 ) ,  pp.  74-85. 

(19)  HARTOG,  P.  J.,,  "A  first  foreshadowing  of  the  periodic  law,"  Nature,  41,  186-8 

(Dec.  26,1889). 

(20)  MENDELEEV,  D,,  "The  periodic  law  of  the  chemical  elements/'  J.  Chem   Soc., 

55,  634-56  (1889). 


668  DISCOVERY  OF  THE  ELEMENTS 

(21 )  "Chemical  Society  Memorial  Lectures,  1901-1913,"  Gurney  and  Jackson,  1914, 

pp.  125-53     Mendeleev  Memorial  Lecture  by  W.  A.  TILDEN. 

(22)  CHEMNITIUS,  F  ,  "Die  Chemie  in  Jena  von  Rolfmck  bis  Knorr  (1629-1921)," 

Verlag  der  Frommannschen  Buchhandlung,  Walter  Biedermann,  Jena,  1929, 
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(23)  SCHIFF,  J.,  "Briefwechsel  zwischen  Goethe  und  Johann  Wolfgang  Dobereiner 

( 1810-1830 )/'  Hermann  Bohlaus  Nachfolger,  Weimar,  1914.,  144  pp. 

(24)  DOBLING,  H  ,  "Die  Chemie  in  Jena  zur  Goethezeit/'  Verlag  von  Gustav  Fischer, 

Jena,  1928,  220  pp 

(25)  TILDEN,  W.  A ,  "Famous  Chemists     The  Men  and  Their  Work/'  George  Rout- 

ledge  and  Sons,  London,  1921,  pp.  241-58. 

(26)  MEYER,  LOTHAR,  "Die  Norur  der  chemischen  Elemente   als  Funktion  ilirer 

Atomgewichte/'  Ann,,  Supplementband  VII,  1870,  354-64  (Heft  3). 
(26)      MEYER,  LOTHAR,   "Die  Natur  der  chemischen  Elemente   als   Funktion  ihrer 
York  City,  1916,  pp.  546-7. 

(28)  "Classics  of  science.   Periodic  law  of  the  elements/'  Sci,  News  Letter,  14?  41-2 

(July  21,  1928).    Mendeleev's  Faraday  Lecture. 

(29)  MEYER,  LOTHAR,  "Die  Anfange  des  naturhchen  Systemes  der  chemischen  Ele- 

mente. Abhandlungen  von  J.  W.  Dobereiner  und  Max  Pettenkofer,"  Ost- 
walds  Klassiker.  Verlag  von  Wilhelm  Engelmann,  Leipzig,  1895,  pp.  3-8, 
27-34. 

(50)  SEUBERT,  "Das  Naturliche  System  der  Chemischen  Elemente.     Abhandlungen 

von  Lothar  Meyer  und  D  Mendeleeff/"  Ostwalds  Klassiker  Verlag  von 
Wilhelm  Engelmann,  Leipzig,  1895,  134  pp. 

(51 )  MONTGOMERY,  J.  P  ,  "Dobereiner's  triads  and  atomic  numbers,"  /.  Chem  Educ  , 

8,162  (Jan.,  1931) 
(32)     REINMUTH,  O.,  "The  structure  of  matter.     II      The  periodic  classification  of 

the  elements,"  J.  Chem.  Educ,  5,  1312-20  (Oct.,  1928), 
(S3)     BUGGE,  G.,  "Das  Buch  der  grossen  Chemiker,"  Vol   2,  Verlag  Chemie,  Berlin, 

1930,  pp.  230-41.    Article  on  Lothar  Meyer  by  P.  WALDEN. 

(34)  Ibid.,  pp.  241-50     Article  on  Mendeleev  by  P.  WALDEN. 

(35)  DE  BOISBAUDRAN,   P.   E.   L.   and  DE   LAPFARENT,   "Sur  une  reclamation   de 

priorite"  en  faveur  de  M.  de  Chancourtois,  relativement  aux  relations  nume- 
riques  des  poids  atomiques,"  Compt.  rend.,  112,  80  (Jan.  12,  1891), 

(36)  W.  A.  T.,  "John  A  R.  Newlands/'  Nature,  58,  395-6  (Aug.  25,  1898). 

(37)  BRAVNER,  B,,  "D.  I  Mendeleev  as  reflected  in  his  friendship  to  Prof  Bohuslav 

Brauner/'  Collection  Czechoslov  Chem.  Communications,  2,  219-43  ( 1930 ) . 

(38)  SWIATLOWSKY,  E.,  "Mendeleeff  centenary,"  Chem  Met  Eng.,  41S  468-9  (Sept , 

1934) 

(39)  TAYLOR,  W.  H,,  "Lewis  Reeve  Gibbes  and  the  classification  of  the  elements/* 

J.  Chem.  Educ,  18,  403-7  (Sept.,  1941). 

(40)  PANETH,  F    A.,  "Radioactivity  and  *he  completion  of  the  periodic  system," 

Nature,  149,  565  (May  23,  1942). 

(41 )  LEICESTER,  H.  M  ,  "Mendeleev  and  the  Russian  Academy  of  Sciences/*  /.  Chem. 

Educ  ,  25,  439-41  ( Aug  ,  1948). 

(42)  TAYLOR,  W.  H.,  "J.  A.  R.  Newlands:    A  pioneer  in  atomic  numbers/'  J.  Chem. 

Educ,  26,  491-6  (Sept.,  1949). 

(43)  WINDERLICH,  RUDOLF,  "Lothar  Meyer,"  J.   Chem.  Educ.,  27,   365-8    (July, 

1950). 

(44)  PRANDTL,  W,,  "Johann  Wolfgang  Dobereiner,  Goethe's  chemical  adviser,"  /. 

Chem.  Educ ,  27,  176-81  (Apr  ,  1950),  CLUSKEY,  J.  E  ,  "Goethe  and  chem- 
istry, ibid,  28,  536-8  (Oct.,  1951). 


PERIODIC  SYSTEM  OF  THE  ELEMENTS  669 

(45)  McPnEBSON,    WILLIAM,    "Chemistry    and    Education,"    Science,    72,   485-93 

(1930),  see  also  Ind  Eng  Chem.,  22,  1028  (1930). 

(46)  LEICESTER,  HENRY  M.s  "Factors  which  led  Mendeleev  to  the  periodic  law," 

CHYMIA,  1,  67-74  (1948). 


Dmitri  Ivanovich  Mendeleev.,  1834-1907.  Professor  of  chemistry  at 
the  University  of  Petrograd.  Author  of  the  "Principles  of  Chemistry,"  a 
remarkable  textbook.  He  studied  the  important  oil  fields  of  Russia  and 
the  United  States.  The  periodic  system  of  the  elements  was  discovered 
independently  by  Mendeleev  in  Russia  and  Lothar  Meyer  in  Germany. 


Die  wirklich  erfolgreiche  Durchfuhrung  anorganisch- 
chemischer  Arbeiten  ist  nur  demjenigen  moglich,  der 
nicht  allein  theoretischer  Chemiker,  sondern  ouch 
vollendeter  Analytiker  ist,  und  zwar  nicht  nur  ein 
praktisch  angelernter  mechanischer  Arbeiter,  sondern 
ein  denkender,  gestaltender  Kiinstler 


*The  truly  successful  performance  of  researches  in  in- 
organic chemistry  is  possible  only  to  one  who  is  not 
only  a  theoretical  chemist  but  also  an  accomplished 
analyst  and,  moreover,  not  merely  a  practically 
trained,  mechanical  worker,  but  a  thinking,  creative 
artist. 

Reinheit  der  Substanzen  ist  die  Feinheit  des  Ganzen 
(6). 

On  the  purity  of  substances  depends  the  perfection 
of  the  whole. 


25 


Some  elements  predicted  by  Mendeleev 


Three  of  the  undiscovered  elements  whose  properties  Mendeleev 
foretold  in  great  detail,  ekaaluminum,  ekaboron,  and  ekasilicon, 
were  discovered  within  fifteen  years  from  the  time  of  their  pre- 
diction. The  first  was  found  by  Lecoq  de  Boisbandran  in  France, 
the  second  by  Lars  Frednk  Nilson  in  Sweden,  and  the  third  bij 
Clemens  Winkler  in  Germany.  These  elements  were  named 
gallium,  scandium,  and  germanium  in  honor  of  these  countries. 


hen  Mendeleev  predicted  that  occupants  would  be  found 
for  the  vacant  spaces  in  the  periodic  system,  he  little  dreamed  that  three 
of  them  would  be  discovered  during  his  lifetime. 

GALLIUM 

One  of  these  elements,  which  he  called  ekaaluminum.,  was  soon  re- 
vealed by  Lecoq  de  Boisbaudran  in  a  mineral  which  Georgius  Agricol  i 
used  to  call  galena  inanis,  or  useless  lead  ore,  and  which  Georg  Brandt 
in  his  dissertation  on  the  half -metals  proved  to  be  a  zinc  mineral  (37,  33). 
It  is  now  known  as  sphalerite,  zinc  sulfide,  or  blende,  and  often  contains 
both  indium  and  gallium  (ekaaluminum).  Paul-Emile  (dit  Frangois) 
Lecoq  de  Boisbaudran  was  born  in  Cognac  on  April  18,  1838,  a  descend- 
ant of  the  Protestant  nobility.  His  father  and  brothers  were  distillers, 
and  Paul-fimile  also  in  time  became  a  member  of  the  firm.  His  mother,  a 
gifted,  well-educated  woman,  taught  him  foreign  languages,  the  classics, 
and  history.  By  studying  the  syllabi  of  the  Ecole  Polytechnique,  he 
acquired  a  splendid  scientific  foundation,  especially  in  his  favorite 
branches,  physics  and  chemistry.  Throughout  his  life  he  was  encouraged 
by  the  sympathy  and  intelligent  aid  of  his  entire  family,  for,  according  to 
Sir  William  Ramsay,  their  watchwords  were  "justice,  kindness,  and  the 
sense  of  personal  responsibility."  An  uncle  helped  him  to  finance  a  small 
private  laboiatoiy,  and  it  was  there  that  ekaalummum,  or  gallium,  was 
discovered  (2). 

The  finding  of  this  element  was  by  no  means  accidental.  Boisbau- 
dran had  been  studying  spectra  for  fifteen  years,  and  had  found  that  in 

671 


672 


DISCOVERY  OF  THE  ELEMENTS 


those  emitted  by  several  metals  of  the  same  family,  the  lines  are  repeated 
according  to  the  same  general  arrangement.  Anxious  to  verify  this  law 
for  the  aluminum  family,  and  to  find  the  missing  member  between  alu- 
minum and  indium,  he  reasoned  that,  since  most  minerals  had  already 
been  carefully  analyzed,  there  was  little  hope  of  finding  new  elements 
among  the  essential  constituents  of  these  minerals.  The  difficulty  of  recog- 
nizing an  unknown  element  present  only  as  a  trace  did  not  escape  him, 
for  he  said,  "The  uncertainty  which  inevitably  reigns  over  the  exact 
chemical  reactions  of  a  hypothetical  substance,  defined  only  by  its  posi- 
tion in  a  natural  series,  renders  quite  problematical  a  success  founded 
solely  on  the  direct  application  of  these  reactions  calculated  in  advance; 
for  the  least  error  in  predicting  one  of  these  can  throw  the  substance  being 
sought  out  of  the  analytical  position  which  theory  assigns  to  it"  (3,  11). 


Lecoq     de     Boisbaudran,     1838-1912. 

French  chemist  who  discovered  gallium, 
samarium,  and  dysprosium,  and  per- 
fected methods  of  separating  the  rare 
earths  He  ranks  with  Buns  en,  Kirch- 
hoff,  and  Crookes  as  one  of  the  founders 
of  the  science  of  spectroscopy, 


In  February,  1874,  Boisbaudran  began  to  investigate  "fifty-two  kilo- 
grams of  blende  of  Pierrefitte  obtained  for  that  purpose  in  the  autumn  of 
1868."  The  Pierrefitte  mine  was  situated  in  the  Argeles  Valley  in  the 
department  of  Hautes  Pyr6n6es  (11, 13).  This  blende  was  given  to  Lecoq 
de  Boisbaudran  by  M.  Malgor,  an  engineer  at  that  mine.  When  Lecoq 
de  Boisbaudran  dissolved  the  ore  and  placed  metallic  zinc  in  the  solution, 
a  deposit  formed  on  the  zinc.  When  he  heated  this  deposit  with  the 
oxyhydrogen  flame  and  examined  it  with  the  spectroscope,  he  saw  two 
lines  that  had  never  been  seen  before.  These,  however,  did  not  appear 
when  he  Heated  the  deposit  simply  with  the  Bunsen  burner, 


SOME  ELEMENTS  PREDICTED  BY  MENDELEEV 


673 


The  following  account  of  the  discovery  was  written  by  Boisbaudran 
himself  for  Chemical  News: 

Between  three  and  four  in  the  evening  of  August  27,  1875,  I  found  indi- 
cations of  the  probable  existence  of  a  new  elementary  body  in  the  products  of 
the  chemical  examination  of  a  blende  from  Pierrefitte,  The  oxide,  or  perhaps 
a  sub-salt,  is  thrown  down  by  metallic  zinc  in  a  solution  containing  chlorides 
and  sulfates.  It  does  not  appear  to  be  the  metal  itself  which  is  reduced  by  the 
zinc  .  .  . 

The  extremely  small  quantity  of  the  substance  at  my  disposal  did  not  per- 
mit me  to  isolate  the  new  body  from  the  excess  of  zinc  accompanying.  The 
few  drops  of  zinc  chloride  in  which  I  concentrated  the  new  substance  gave 
under  the  action  of  the  electric  spark  a  spectrum  composed  chiefly  of  a  violet 
ray,  narrow,  readily  visible,  and  situate  at  about  417  on  the  scale  of  wave 
lengths.  I  perceived  also  a  very  faint  ray  at  404  (4,  16). 


Adolph  Wurtz,  1817-1884.  Professor 
of  chemistry  at  the  ficole  de  Medecine 
in  Paris.  Discoverer  of  methyl  and 
ethyl  amines  and  the  synthesis  of  hydro- 
carbons from  alkyl  iodides  and  sodium. 
He  studied  the  oxidation  products  of  the 
glycols  and  the  homologs  of  lactic  acid 
The  proof  of  the  elementary  nature  of 
gallium  was  demonstrated  in  his  labo- 
ratory by  Lecoq  de  Boisbaudran. 


From  Hofmann's  "Zur  Errnnerung 
an  v&rangegangene  Freunde 


A  month  later  Boisbaudran  performed  in  Wurtz's  laboratory  in  Paris, 
in  the  presence  of  the  chemistry  section  of  the  Institute,  a  series  of  experi- 
ments to  prove  that  gallium,  the  metal  he  had  discovered  and  named  in 
honor  of  France,  is  a  true  element.  In  order  that  he  might  attempt  to 
isolate  the  metal,  the  technical  zinc-mining  societies  known  as  "La  Vieille 
Montagne"  and  "La  Nouvelle  Montague"  presented  him  with  a  quantity 
of  gallium-containing  zinc  minerals. 

Boisbaudran  decomposed  several  hundred  kilograms  of  the  crude 
zinc  blende  in  aqua  regia  containing  excess  hydrochloric  acid.  He  also 


674 


DISCOVERY  OF  THE  ELEMENTS 


used  a  slight  excess  of  blende  in  order  that  all  the  nitric  acid  might  be 
consumed.  After  filtering  off  the  insoluble  matter,  he  placed  sheets  of 
zinc  in  the  acid  filtrate  in  order  that  the  copper,  arsenic,  lead,  cadmium, 
indium,  thallium,  mercury,  selenium,  silver,  bismuth,  tin,  antimony,  and 
gold  might  be  deposited.  Befoie  the  acid  had  been  entirely  consumed 
by  the  zinc,  Boisbaudran  filtered  off  this  spongy  deposit.  By  adding  a 
large  excess  of  zinc  to  the  filtrate,  and  heating  the  mixture  for  several  hours 
on  the  water  bath,  he  was  able  to  precipitate  the  basic  salts  of  zinc  and 
the  hydroxides  of  aluminum,  iron,  gallium,  cobalt,  and  chromium. 


Emile-Clement  Jungfleisch,*  1839- 
1916.  French  chemist  and  pharmacist. 
Professor  of  organic  chemistry  at  the 
Ecole  Superieure  de  Pharmacie  and  at 
the  College  de  France.  Although  most 
of  his  ninety-rune  papers  were  organic 
or  pharmaceutical  in  nature,  he  also 
made  valuable  contributions  to  the 
chemistry  of  gallium  and  indium. 


Although  gallium  sulfide  does  not  precipitate  from  a  solution  of  the 
pure  salt,  it  is  readily  carried  down  with  zinc  sulfide.  Boisbaudran  there- 
fore added  ammonium  acetate  and  acetic  acid  to  the  hydrochloric  acid 
solution  of  the  above  precipitate,  and  passed  in  hydrogen  sulfide.  As 
long  as  the  line  Ga  a  (417  0)  continued  to  show  in  the  spectrum  of  the 
precipitate,  he  kept  on  adding  zinc  to  the  filtrate  until  finally  all  the 
gallium  had  been  precipitated. 

By  dissolving  gallium  hydroxide  in  caustic  potash,  and  electrolyzing 
the  solution  with  a  current  from  five  or  six  Bunsen  cells,  Boisbaudran 
prepared  more  than  a  gram  of  gallium  metal.  This  was  first  prepared  in 
November,  1875.  On  December  6th  he  presented  3.4  milligrams  of  solid 
gallium  (14)  to  the  Academy  of  Sciences,  and  three  months  later  he 

*  The  portrait  of  Jungfleisch  was  obtained  through  the  kindness  of  Dr.  Tenney  L. 
Davis,  Massachusetts  Institute  of  Technology. 


SOME  ELEMENTS  PREDICTED  BY  MENDELEEV 


675 


presented  a  specimen  of  the  liquid  metal.  Since  gallium,  when  free  from 
the  solid  phase,  has  a  great  tendency  to  remain  in  the  superfused  state, 
this  specimen  may  have  remained  liquid  even  at  a  temperature  below 
30°  Centigrade  (17).  Boisbaudran  and  Jungfleisch  afterward  worked  up 
four  thousand  kilograms  of  the  blende  at  the  Javel  works,  and  obtained 
seventy-five  grams  of  the  metal  (18). 


PROPERTIES  PREDICTED  FOR 

EKAALUMINUM  (Ea)   BY 

MENDELEEV 

Atomic  weight  about  68 

Metal  of  specific  gravity  5.9,  melting 
point  low,  non-volatile,  unaffected  by 
air,  should  decompose  steam  at  red 
heat;  should  dissolve  slowly  in  acids 
and  alkalies 

Oxide-  formula  Ea3O3;  specific  gravity 
5.5,  should  dissolve  m  acids  to  form 
salts  of  the  type  EaX,i.  The  hydroxide 
should  dissolve  in  acids  and  alkalies. 

Salts  should  have  tendency  to  form  basic 
salts,  the  sulfate  should  form  alums; 
the  sulfide  should  be  precipitated  by 
H2S  or  (NEU)sS.  The  anhydrous  chlo- 
ride should  be  more  volatile  than  zinc 
chloride. 

The  element  will  probably  be  discovered 
by  spectroscopic  analysis 


PROPERTIES  FOUND  FOR 

BOISBAUDRAN'S 

GALLIUM  (Ga) 

Atomic  weight  69.9  * 

Metal  of  specific  gravity  5.94;  melting 
point  30  15,  non-volatile  at  moderate 
temperature;  not  changed  in  air,  action 
of  steam  unknown;  dissolves  slowly  in 
acids  and  alkalies 

O\ide  Ga»Oa,  specific  gravity  unknown, 
dissolves  in  acids,  forming  salts  of  the 
type  GaXa  The  hydroxide  dissolves 
in  acids  and  alkalies. 

Salts  readily  hydrolyze  and  form  basic 
salts;  alums  are  known;  the  sulfide  is 
precipitated  by  H2S  and  by  (NH4)jS 
under  special  conditions  The  anhy- 
drous chloride  is  more  volatile  than 
zinc  chloride 

Gallium  was  discovered  with  the  aid  of 
the  spectroscope. 


In  discovering  this  element  Lecoq  de  Boisbaudran  was  guided,  not 
by  the  periodic  table  and  the  predictions  of  Mendeleev  but  by  his  own 
law  of  spectra  (31).  On  November  22,  1875,  however,  the  great  Russian 
chemist  stated  in  the  Comptes  rendus  (15)  that  he  believed  gallium  to 
be  identical  with  ekaaluminum  (20).  Further  study  of  the  properties  of 
the  new  element  and  its  compounds  fully  confirmed  this  view  (19).,  as 
is  evident  from  the  foregoing  table.  Lecoq  de  Boisbaudran  also  found 
gallium  in  a  transparent  blende  from  Santander  given  to  him  by  M. 
Friedel  (14).  After  testing  a  large  number  of  blendes  and  products 
of  zinc  works,  Boisbaudran  succeeded  "in  finding  only  two  richer  than 
Pierrefitte  blende;  these  were  the  yellow  transparent  blende  from  Asturias 
and  the  black  blende  from  Bensberg.  All  the  other  substances  I  examined 
were  much  too  poor"  (11).  He  proved  that  the  gallium  had  come  from 
the  blendes  themselves  and  not  from  the  Vieille  Montagne  metallic  zinc 
used  in  the  precipitations  (14).  Georges  Urbain  and  his  collaborators 
found  gallium  in  59  of  the  64  blendes  which  they  examined  (3,9). 

*  The  1955  atomic  weight  of  gallium  is  69,72. 


676  DISCOVERY  OF  THE  ELEMENTS 

Boisbaudran's  researches  on  the  rare  earths  also  yielded  a  rich  harvest 
of  results,  for  he  discovered  samarium  and  dysprosium  (2).  His  investi- 
gations in  the  field  of  spectroscopy  were  also  of  high  merit 

Boisbaudran  spoke  English  fluently,  but  without  regard  for  fine  dis- 
tinctions, and  he  sometimes  made  the  mistake  of  translating  his  French 
thoughts  too  literally.  According  to  Sir  William  Ramsay,  he  once  startled 
his  dinner  partner,  a  dignified,  elderly  English  lady,  with  the  remark, 
"The  soup  is  devilish  hot/'  Like  Berzelius,  he  married  late  in  life.  His 
contributions  to  science  were  cut  short  by  the  pain  and  disability  resulting 
from  severe  anchylosis  of  the  joints,  but  he  stoically  bore  this  misfortune 
for  many  years  until  death  relieved  him  on  May  28,  1912,  at  the  age  of 
seventy-four  years  (2,  12). 

Although  gallium  is  one  of  the  rarest  of  elements,  it  has  an  interesting 
use.  Since  it  melts  at  about  30°  Centigrade  and  boils  at  about  1700°, 
a  gallium-in-quartz  thermometer  can  be  used  for  measuring  high  tempera- 
tures far  above  the  range  of  the  ordinary  mercury-in-glass  thermometer. 
Unfortunately,  it  differs  from  mercury  in  that  it  wets  glass  and  quartz 
surfaces  (40,  41}. 

Gallium  often  occurs  closely  associated  with  aluminum.  Sir  Walter 
N.  Hartley  and  H.  Ramage  detected  it,  in  1897,  in  all  the  specimens  of 
bauxite,  kaolin,  and  aluminous  iron  ores  which  they  analyzed  (42).  They 
found  that  the  blast-furnace  iron  smelted  at  Middlesbrough  on  Tees  from 
the  Yorkshire  clay-ironstone  contained  even  more  gallium  than  the  Bens- 
berg  blende  from  the  Franzisca  adit  of  the  Ludench  mine  near  Cologne, 
which  had  previously  been  the  richest  known  source  of  that  metal  (43). 
They  also  detected  gallium  in  feldspar,  mica,  basalt,  pumice  from  Kraka- 
toa,  volcanic  dust  from  New  Zealand,  and  meteoric  iron  and  dust  (42,  43), 

In  about  1915  F.  G.  McCutcheon,  chemist  of  the  Bartlesville  Zinc 
Company  of  Oklahoma,  presented  some  gallium  of  American  production 
to  W.  F.  Hillebrand  and  J.  A.  Scherrer  for  analysis,  According  to  Mr, 
Kurt  Stock,  superintendent  of  this  company,  Mr.  McCutcheon  had  ob- 
served "peculiar  beads  and  drops,  in  appearance  like  mercury,  which 
seemed  to  sweat  out  of  zinc-lead  dross  plates  after  these  had  been  ex- 
posed to  the  weather  for  a  time/'  Mr.  McCutcheon  and  his  assistants 
proved  that  this  was  an  alloy  of  gallium  and  indium  with  small  amounts 
of  zinc.  The  great  demand  at  that  time  for  high-grade  spelter  (metallic 
zinc)  "had  led  zinc  smelters  to  the  practice  of  redistillation,  and  it  is 
the  final  leady  residue  from  such  continued  redistillation  that  carries 
gallium  in  noticeable  quantities  .  .  ."  (40).  This  gallium  was  known  to 
come  from  domestic  ores,  probably  from  the  Joplin  area  (40,  44,  45). 

W.  Feit,  in  his  unsuccessful  search  for  ekamanganese  (element  43) 
in  1933;  unexpectedly  found  galljurn  in  several  of  the  intermediate  prod- 


SOME  ELEMENTS  PREDICTED  BY  MJSNDELEEV 


677 


ucts  from  the  working  of  cupriferous  slate  from  Mansfeld,  and  developed 
its  commercial  production  (41,  44). 

According  to  J.  Papish  and  C.  B.  Stilson,  the  zinc  minerals  sphalerite, 
gahnite,  hopeite,  parahopeite,  and  adamite  all  contain  gallium  (44,46}. 
It  has  also  been  detected  spectroscopically  in  certain  French,  Spanish, 
and  Japanese  mineral  waters  (47 \  48).  Germanite  from  Tsumeb,  South- 
west Africa,  contains  from  0.57  to  1.85  per  cent  of  gallium  and  is  thus 
a  rich  source  of  this  rare  metal  (44,49). 


SCANDIUM 

Mendeleev  had  predicted  that  another  element,  which  he  called 
ekaboron  and  which  he  said  would  have  an  atomic  weight  between  40 
(calcium)  and  48  (titanium),  would  some  day  be  revealed  (20).  It  was 
discovered  in  1879  by  Lars  Fredrik  Nilson. 

Euxenite,  the   original  source   of   scandium    (ekaboron),  was   dis- 


Lars  Fredrik  Nikon,  1840-1899.  Pro- 
fessor of  analytical  chemistry  at  the  Uni- 
versity of  Upsala  and  at  the  Agricultural 
Academy  at  Stockholm.  Discoverer  of 
scandium  His  researches  on  soils  and 
fertilizers  transformed  the  barren  plains 
of  his  native  island  into  an  agricultural 
region  With  Otto  Pettersson  he  in- 
vestigated the  rare  earths  and  prepared 
metallic  titanium. 


From  A.  G.  Ekstrand's  Minnesteckrang 


678 


DISCOVERY  OF  THE  ELEMENTS 


covered  by  C.  J,  A.  Theodor  Scheerer  (1813-1875).  He  was  educated  at 
the  University  of  Berlin  and  the  Freiberg  School  of  Mines,  and  for  several 
years  taught  metallurgy  and  assaying  at  the  University  of  Chnstiania. 
In  1840  he  published  in  PoggendorfFs  Annalen  the  first  description  of 
euxenite,  a  new  mineral  found,  first  near  Jolster  in  northern  Bergenhuus- 
Amt  and  later  at  Tvedestrand  near  Arendal,  Norway  (50,  51). 

The  specimen  Scheerer  analyzed  was  given  to  him  by  Professor 
B,  M.  Keilhau  (51).  Using  a  very  small  sample,  Scheerer  made  an 
appioximate  quantitative  analysis,  from  which  he  reported  the  presence 
of  tantalic  and  titanic  acids,  yttria,  uranous,  cerous,  and  lanthanum  oxides, 
lime,  magnesia,  and  water.  He  named  the  mineral  euxenite  because  of 


Berzelius*  at  the  Age  of  Forty-Four 
Years,  This  represents  him  as  he  ap- 
peared in  1823  when  the  youthful  Fried- 
rich  Wohler  came  to  Stockholm  to  study 
chemistry. 


its  many  rare  constituents.  He  believed  it  to  be  closely  related  to  yttro- 
tantalite,  yet  different  from  it  in  specific  gravity,  in  water  content,  and 
in  the  presence  of  titanic  acid,  cerium,  and  lanthanum  among  its  con- 
stituents (51). 

L.  F.  Nilson  was  born  on  May  27,  1840,  in  Ostergotland,  was  educated 
at  Visby  and  at  the  Linkoping  Gymnasium,  and  at  the  age  of  nineteen 
yeais  went  to  Upsala  to  study  biology,  chemistry,  and  geology.  Just  as 
he  was  ready  to  take  his  examinations  for  the  doctorate  in  1865,  he 
received  word  that  his  father  had  been  seriously  injured.  Although 
Lars  Nilson  himself  was  then  in  very  poor  health,  and  suffering  from 
frequent  hemorrhages  from  the  lungs,  he  immediately  returned  to  Goth- 
land Island,  took  charge  of  the  farm,  purchased  an  engine  and  a  threshing 

*  Reproduced  from  H,  G.  Soderbaum's  "Jac.  Berzelius-Levnadsteckning"  by  kind  per- 
mission of  the  author. 


SOME  ELEMENTS  PREDICTED  BY  MENDELEEV 


679 


machine,  harvested  the  crops,  and  cheered  and  encouraged  his  sick 
father.  After  a  few  months,  both  father  and  son  were  in  good  health. 
Life  in  the  open  air  had  quickly  cured  Nilson's  lung  trouble,  and  he 
enjoyed  good  health  for  the  rest  of  his  life  (5). 

He  returned  to  Upsala,  passed  his  examinations  successfully,  and  was 
placed  m  charge  of  the  laboratory.  Here,  among  Berzelius*  balances, 
blowpipes,  and  preparations,  he  became  a  true  disciple  of  that  great 
master.  After  completing  some  researches  on  the  compounds  of  selenium, 
Nilson  and  Pettersson  began  to  study  the  mineral  euxenite,  hoping  to 
measure  the  chemical  and  physical  constants  of  the  rare  earth  elements 


Inside  the  City  Wall  of  Visby.*     Lars  Fredrik  Nilson,  the  discoverer  of 
scandium,  received  his  early  education  in  tins  beautiful  old  city  on  Gothland 

Island. 


and  their  compounds  and  thus  to  verify  the  periodic  law.  Although 
they  never  succeeded  in  this,  Nilson  extracted  sixty-three  grams  of  the 
rare  earth  erbia  from  gadolinite  and  euxenite,  and  converted  it  into  the 
nitrate,  Upon  decomposing  this  salt  by  heat,  as  Marignac  had  done,  he 
obtained  some  very  pure  ytterbia  and,  to  his  great  surprise,  a  feebly  basic 
earth  that  was  unknown  to  him  (21). 

Upon  thoroughly  investigating  this  new  earth,  he  found  that  it  con- 
tained an  element  whose  properties  coincided  almost  exactly  with  those 
Mendeleev  had  predicted  for  ekaboron.  P.  T.  Cleve  had  also  encountered 

*  Photo  by  Miss  Mary  Larson,  Dept.  of  Zoology,  The  University  of  Kansas. 


680  DISCOVERY  OF  THE  ELEMENTS 

the  same  substance  in  his  researches  on  the  rare  earths.  Since  this  ele- 
ment was  first  discovered  in  the  minerals  euxenite  and  gadolinite  which 
had  not  yet  been  found  anywhere  except  in  Scandinavia,  Nilson  called  it 
scandium  (22)  in  honor  of  his  fatherland,  and  it  was  indeed  appropriate 
that  it  should  be  named  for  the  little  country  where  so  many  new  ele- 
ments had  been  discovered  (6). 

By  working  up  ten  kilograms  of  euxenite,  some  of  Cleve  s  ytterbia 
from  gadolinite,  and  some  ytterbia  residues  from  keilhauite,  Nilson  pre- 
pared about  two  grams  of  scandium  oxide  of  high  purity  (34) .  "When  I 
began  this  work,"  said  he,  "I  had  at  my  disposal  63  g.  of  erbia  of 
molecular  weight  129.25  which  had  been  extracted  partly  from  gadolinite 
and  partly  from  euxenite"  (21,  22).  Although  Nilson  was  at  first  in- 
clined to  believe  that  scandium  was  present  only  in  the  euxenite,  T.  R. 
Thalen  observed  one  of  the  spectral  lines  of  scandium  in  a  mixture  of 
erbium  and  yttrium  prepared  from  gadolinite  by  Hoglund  and  Cleve 
(21,  22).  The  identity  of  scandium  and  Mendeleev's  hypothetical  eka- 
boron  was  pointed  out  by  Per  Theodor  Cleve  (20,  25).  The  table 
below  shows  the  predicted  and  observed  properties  of  this  element  (19). 

PROPERTIES   PREDICTED   FOR  PROPERTIES  FOUND 

EKABORON  (Eb)  BY  FOR  NELSON'S 

MENDELEEV  SCANDIUM  (Sc) 

Atomic  weight  44.  Atomic  weight.* 

It  will  form  one  oxide  Eba03  of  specific  Scandium  oxide,  ScoOs,  has  a  specific 
gravity  3  5,  more  basic  than  alumina,  gravity  of  3  86,  is  more  basic  than 
less  basic  than  yttria  or  magnesia,  not  alumina,  less  basic  than  yttria  or  mag- 
soluble  m  alkalies;  it  is  doubtful  if  it  nesia.  It  is  not  soluble  in  alkalies  and 
will  decompose  ammonium  chloride.  does  not  decompose  ammonium  chlo- 

The  salts  will  be  colorless  and  give  gelati-  ride                                                         ^ 

nous   precipitates   with  potassium  hy-  Scandium    salts    are    colorless,    and    give 

droxide  and   sodium   carbonate      The  gelatinous  precipitates  with  potassium 

salts  will  not  crystallize  well.  hydroxide  and  sodium  carbonate.    The 

The  carbonate  will  be  insoluble  in  water;  sulfate  crystallizes  with  difficulty, 

and  probably  be  precipitated  as  a  basic  Scandium  carbonate  is  insoluble  in  water. 

sajt  and  readily  loses  carbon  dioxide. 

The  double  alkali  sulfates  will  probably  The  double  alkah  sulfates  are  not  alums, 

nut  be  alums  Scandium  chloride,  ScCla,  begins  to  sub- 

The  anhydrous  chloride,  EbCL  should  be  nme  at  850'.     Alummum  crJoride  be- 
less  volatile  than   aluminum   chloride,  gms  to  sublime  above  100  .  In  aqueous 
and   its    aqueous   solution  should  hy-  solution  the  salt  is  hydrolyzed. 
drolyze  more  readily  than  that  of  mag-  Scandium  was  not  recognized  by  spec- 
nesium  chloride.  trum  analysis. 

Ekaboron  will  probably  not  be  discovered 
spectroscopically. 

The  spectra  of  scandium  and  ytterbium  were  first  studied  by  Tobias 
Robert  Thalen  (22,  32).     Although  scandium  salts  possess  no  visible 

*  The  1955  atomic  weight  of  scandium  is  44.96. 


SOME  ELEMENTS  PREDICTED  BY  MENDELEEV 


681 


absorption  spectrum,  the  element  may  be  detected  by  means  of  spark  and 
arc  spectra  (24,  33).  The  atomic  weights  of  both  these  elements  were 
soon  determined  by  Nilson  (23). 

From  1878  to  1883  Nilson  served  as  professor  of  analytical  chemistry 
at  the  University  of  Upsala,  but  in  his  later  years  he  taught  at  the  Agri- 
cultural Academy  at  Stockholm.  He  found  that  the  sterility  of  the 
calcareous  moors  of  his  native  island  was  caused  by  lack  of  potash.  After 
liberal  use  of  kainite  fertilizer,  recommended  by  Nilson,  Gothland  Island 
began  to  yield  good  crops  of  sugar  beets  (6). 


Tobias     Robert     Thalen,     1827-1905. 

Swedish  physicist,  astronomer,  and  spec- 
troscopist.  He  mapped  the  spectra  o£ 
yttrium,  erbium,  didymium,  lanthanum, 
scandium,  thulium,  and  ytterbium,  and 
in  1866  wrote  a  historical  review  of 
spectrum  analysis.  He  also  studied  the 
magnetic  properties  of  iron  and  iron 
ores. 


From  Hasselbergs,  "Biografi&r   T    R    Thalcn" 


A.  G.  Ekstrand,  in  his  biography  of  Nilson  written  for  the  Swedish 
Academy  of  Sciences,  expressed  admiration  that  "A  person  can  work 
with  chemicals  and  chemical  apparatus  in  such  a  neat  and  truly  elegant 
manner  as  he  does.  In  the  laboratory  at  Upsala,  where  I  worked  beside 
him  for  many  years,  I  cannot  recall  ever  having  seen  him  in  a  laboratory 
coat"  (34).  Ekstrand  described  Nilson  as  a  practical  chemist,  not  much 
given  to  theorizing. 

Nilson's  long  hours  in  the  laboratory  left  him  little  time  for  recrea- 
tion, but  his  brief  periods  of  relaxation  were  free  from  worry,  Otto 
Pettersson,  professor  of  chemistry  at  the  University  of  Stockholm,  once 
said  of  him: 


682 


DISCOVERY  OF  THE  ELEMENTS 


Whilst  it  was  customary,  in  the  private  laboratory  where  Nilson  presided, 
to  enliven  the  hours  of  work  with  conversation,  anecdotes,  puns,  occasionally 
by  a  song,  etc.,  it  was  considered  unfitting  to  introduce  scientific  matters  into 
the  conversation  of  leisure  hours  Nilson  positively  did  not  admit  it,  and  woe 
to  him  who  dared  to  speak  of  political  or  philosophical  matters  when  Nilson 
intended  to  be  merry.  And  he  was  always  meiry  when  he  was  with  his  friends, 
the  merriest  of  them  all.  He  had  a  thousand  devices  for  putting  a  stop  to  a 
conversation  which  threatened  to  take  a  tiresome  turn.  He  would,  for  example, 
sit  listening  for  a  while  with  a  grave  face,  and  then  interpose  with  a  short 
nonsensical  observation,  delivered  with  great  solemnity  in  the  accents  of  some 
political  or  scientific  worthy  of  pedantic  fame,  while  a  gleam  of  fun  shot  forth 
from  under  his  heavy,  dusky  eyebrows.  The  effect  was  irresistibly  comic,  so 
much  the  more  as  it  came  unforeseen  His  hearers  were  at  first  puzzled,  then 
one  chuckled,  another  laughed,  and  in  a  minute  the  impending  political  or 
philosophical  discourse  was  drowned  in  a  chorus  of  laughter  in  which  Nilson's 
voice  at  last  joined  in  accents  swelling  like  big  waves  and  rollers  of  an  ocean 
of  mirth  (5). 


Old  Apothecary  Shop  at  Visby* 

*  Photo  loaned  by  Miss  Mary  Larson,  Dept  of  Zoology,  The  University  of  Kansas. 


SOME  ELEMENTS  PREDICTED  BY  MENDELEEV 


683 


Like  all  successful  analysts,  Nilson  had  a  passion  for  neatness  and 
order,  and  his  motto,  "On  the  purity  of  substances  depends  the  perfection 
of  the  whole"  is  well  worth  remembering  (6).  He  died  on  May  14, 
1899,  at  the  age  of  fifty-nine  years  (34). 

Until  the  end  of  the  nineteenth  century,  scandium  was  believed  to 
be  one  of  the  rarest  of  elements,  but  in  1908  Sir  William  Crookes  and 
G.  Eberhard  found  small  amounts  of  it  to  be  widely  distributed  on  the 
earth,  the  sun,  and  other  heavenly  bodies  (34), 

GERMANIUM 

A  third  element  that  Mendeleev  had  predicted  was  to  be  a  member 
of  the  silicon  family  (20).  This  "ekasilicon"  was  discovered  in  1886 
by  Clemens  Wmkler,  who  named  it  germanium  in  honor  of  his  fatherland. 
Thus  the  three  "nationalist"  elements— gallium  in  France,  scandium  in 


Clemens  Alexander  Winkler*  1838-1904. 
Professor  o£  chemistry  at  the  Freiberg 
School  of  Mines  Pioneer  in  the  analysis 
of  gases.  Manufacturer  of  nickel  and  co- 
balt He  discovered  the  element  germa- 
nium and  made  pioneer  researches  on 
indium 


Sweden,  and  germanium  in  Germany— were  all  discovered  within  fifteen 
years  after  their  prediction  by  the  great  Russian  chemist.  Although 
Mendeleev  was  the  first  person  to  describe  the  properties  of  ekasilicon, 
the  gap  in  the  periodic  table  had  been  observed  about  seven  years 
before  by  the  English  chemist  J.  A.  R  Newlands,  who  had  noticed  that 
silicon  and  tin  form  the  extremities  of  a  triad,  the  middle  member  of 
which  was  missing  (29). 

*  This  photograph  of  Winkler  was  made  by  Dr,  O,  Brunck,  Rector  of  the  Freiberg 
School  of  Mines,  who  graciously  sent  Dr.  Dains  a  copy. 


684  DISCOVERY  OF  THE  ELEMENTS 


r~ 


Courtesy  S    G.  Sjoberg 

Nils  Gabriel  Sefstrbm,  1787-1845.  Swedish  physician,  chem- 
ist, and  metallurgist.  Head  teacher  at  the  School  of  Mines  at 
Falun  from  1822  to  1838,  later  adviser  to  the  Mining  Society  in 
Stockholm,  director  of  the  Mineral  Cabinet,  Chemical  Labora- 
tory, and  Library  of  the  Royal  Mining  College,  and  editor  of 
the  Annals  of  the  Corporation  of  Ironmasters  See  ref.  (59) 


Clemens  Alexander  Winkler  was  born  at  Freiberg  on  December  26, 
1838,  but  grew  up  in  Zschopenthal,  a  village  in  the  Saxon  Erzgebirge 
where  his  father,  Kurt  Alexander  Winkler,  operated  a  smalt  works.  Kurt 
Winkler  was  himself  a  well-known  chemist  and  metallurgist,  who  had 
studied  under  Berzelius  and  N.  G.  Sefstrom,  and  had  fitted  up  an  excel- 
lent metallurgical  laboratory  in  the  smalt  works  (7,  30). 

Since  the  son  soon  learned  to  love  Nature,  his  father  taught  him  to 
identify  and  classify  plants,  animals,  and  minerals.  The  boy,  however, 
never  acquired  a  passion  for  collecting.  He  wanted  to  learn  as  much  as 


SOME  ELEMENTS  PREDICTED  BY  MENDELEEV  685 

possible  about  each  specimen,  but  had  no  desire  to  own  it  At  the  age 
of  twelve  years  he  entered  the  Freiberg  gymnasium,  where  he  studied 
mineralogy  under  August  Breithaupt.  Wmkler  did  not  like  foreign 
languages,  but  nevertheless  acquired  such  a  thorough  mastery  of  his 
mother  tongue  that  his  scientific  papers  are  valued  not  only  for  their 
genuine  scientific  merit  but  also  for  their  beautiful,  faultless  German  (7). 
He  continued  his  education  at  the  Realschule,  or  scientific  school,  at 
Dresden  and  at  the  Gewerbeschule,  or  technical  school,  in  Chemnitz, 
spending  the  vacations  in  his  father's  laboratory.  When  he  entered  the 
Freiberg  School  of  Mines  in  1857,  he  already  knew  more  analytical  chem- 
istry than  was  taught  there,  and  because  of  this  thorough  preparation 
and  his  sound  constitution,  he  was  able  to  make  remarkable  progress  in 
research  without  missing  any  of  the  dances  and  gay  parties  so  dear  to 
a  student's  heart  (7). 


Portrait  Medallion  of  Berzelius  by  David 
<T  Angers,   1835,* 


His  paper  on  the  reactions  that  take  place  in  the  Gay-Lussac  towers 
of  sulfuric  acid  plants  resulted  from  his  successful  experiments  on  the 
absorption  of  obnoxious  sulfur  dioxide  fumes  from  an  ultramarine  plant. 
In  order  to  analyze  the  gases,  he  invented  the  Winkler  gas  buret  with  a 
three-way  stopcock,  and  perfected  his  own  methods.  In  the  meantime 
he  made  his  living  by  producing  nickel  and  cobalt  on  a  commercial  scale. 

In  1873  he  accepted  a  position  as  professor  of  chemical  technology 
and  analytical  chemistry  at  Freiberg.  G.  D.  Hinrichs  once  said,  "The 
perfection  of  the  analytical  work  of  Winkler  astonished  me  till  I  found 
the  name  of  his  father,  Kurt  Winkler,  in  the  list  of  special  students  of 
Berzelius"  (8).  Winkler,  who  had  learned  neatness  from  his  father, 

*  Reproduced  from  H.  G  Soderbaum's  "lac.  Berzehus-Levnadsteckning"  by  kind  per- 
mission of  the  author. 


686 


DISCOVERY  OF  THE  ELEMENTS 


soon  transformed  the  slovenly  laboratories,  and  trained  his  students  to 
work  so  carefully  that  rubber  aprons  were  not  needed.  One  day,  when 
a  new  student  appeared,  wearing  a  large  apron,  Winkler  exclaimed,  "And 
so  you're  going  to  mix  lime"  (7). 

In  the  fall  of  1885  there  was  found,  at  the  approach  of  a  vein  in 
the  Himmelsfurst  mine  near  Freiberg,  a  new  ore  which  the  discoverer, 
Albin  Weisbach,,  a  professor  of  mineralogy  at  the  Freiberg  School  of 
Mines,  named  argyrodite  (28).  Hieronymus  Theodor  Richter,  the 
chemist  who  with  Ferdinand  Reich  had  discovered  indium,  made  a 


Albin  Weisbach  1833-1901.  German 
mineralogist,  crystallographer,  and  physi- 
cist Discoverer  of  argyrodite,  the  min- 
eral in  which  Clemens  Winkler  afterward 
discovered  germanium  He  was  a  son  of 
Julius  Weisbach,  the  distinguished  mining 
engineer,  and  a  student  of  Ferdinand 
Reich,  the  discoverer  of  indium. 


From  Goldschmidt's  "Ennnentngsblatter 
an  Albin  Weisbach" 


qualitative  blowpipe  analysis  of  the  argyrodite,  and  found  that  it  con- 
tained silver,  sulfur,  and  a  trace  of  mercury  (27).  Professor  Weisbach 
then  asked  Winkler  to  make  a  thorough  quantitative  analysfe  in  order  to 
establish  the  composition  of  the  mineral. 

"In  the  middle  of  last  September  [1885],"  said  Weisbach,  "in  the 
famous  old  Himmelsfurst  Mine  at  St.  Michaelis  near  Freiberg,  in  passage 
number  lOVs,  four  hundred  and  sixty  meters  under  ground,  at  an  inter- 
section of  the  shaft  of  the  silver  mine  with  an  unknown  spar,  there  oc- 
curred a  break  which  yielded,  among  other  things,  an  ore  which  attracted 
the  attention  of  Mine  Manager  and  Director  Neubert,  who  therefore 
sent  a  specimen  of  it  to  Herr  Wappler,  director  of  the  mineral  depot  at 
the  Mining  Academy,  with  the  notation  that  the  ore  in  question  indeed 


SOME  ELEMENTS  PREDICTED  BY  MENDELEEV  687 

bore  some  resemblance  to  silver  glance  [Silberkies],  yet  seemed  to 
differ  from  it.  Foreman  Wappler,"  continued  Weisbach,  "also  became 
convinced  of  these  differences  and  therefore  gave  Superintendent  Th 
Richter  a  specimen  of  it  for  analysis.  The  latter  established  silver  and 
sulfur  as  the  main  constituents.  .  .  ." 

"Herr  Wappler,"  said  Weisbach,  "kindly  sent  word  to  me  in  Eisenerz, 
Steiermark  and,  on  my  return  to  Freiberg,  gave  me  a  larger  number  of 
specimens  from  the  Himmelsfurst  break.  At  the  meeting  of  our  mining 
society  on  October  first,  I  was  therefore  able  to  give  a  short  description 
of  the  new  mineral,  which  I  called  argyrodite,  a  few  specimens  of  which 
were  already  in  circulation;  on  October  15th  I  showed  the  members  of 
the  society  a  wooden  model  representing  the  crystal  form  of  the  argyro- 
dite. .  .  . 

'Th,  Richter,"  said  Weisbach.  "had  already  determined  the  silver 
content  in  two  concordant  blowpipe  analyses  as  73V2  per  cent.  My 
colleague  Cl.  Winkler  then  obtained  as  the  mean  of  several  experiments 
75  per  cent  of  silver  and  18  of  sulfur,  hence  a  loss  of  7  per  cent.  This 
loss,  after  long  remaining  inexplicable,  finally  led,  in  the  course  of  further 
investigations,  to  the  discovery  of  a  new  element  similar  in  properties 
to  arsenic  or  antimony,  which  Winkler,  the  discoverer,  on  February  1st 
named  germanium"  (28). 

The  argyrodite  consisted  of  fine,  steel-gray  crystals  resembling  silver 
pyrite,  and  formed  a  thin  layer  over  the  impure  ore,  which  consisted 
mainly  of  siderite,  pyrite,  red  silver  ore,  and  argentine  (55).  Even  in  his 
first  researches  on  germanium,  Winkler  was  hampered  by  lack  of  sufficient 
argyrodite,  and  the  supply  of  this  mineral  at  Freiberg  soon  became 
exhausted. 

Winkler's  results  were  consistent,  but,  since  they  invariably  came  out 
7  per  cent  too  low,  he  concluded  that  the  ore  must  contain  an  unknown 
element*  (26).  Believing  that  the  mineral  must  be  a  sulfo  salt  of  silver 
and  that  the  new  element  must  belong  in  the  same  analytical  group  with 
arsenic,  antimony,  and  tin,  he  fused  a  pulverized  portion  with  sodium 
carbonate  and  sulfur,  took  up  the  melt  with  water,  and  filtered  off  the 
residue.  By  making  the  filtrate  slightly  acidic  with  hydrochloric  acid, 
he  precipitated  and  removed  the  sulfides  of  arsenic  and  antimony.  Now, 
since  the  new  element  had  not  been  removed  with  any  of  the  precipitates, 
it  would  have  to  be  present  in  the  filtrate  as  a  sodium  sulfo  salt.  Yet 
when  Winkler  added  a  little  more  hydrochloric  acid,  a  precipitate  con- 
taining free  sulfur,  but  no  sulfide,  was  thrown  down.  Even  upon  evaporat- 
ing the  filtrate  to  dryness,  he  obtained  nothing  but  sodium  chloride. 

*  The  reader  will  recall  that  similar  results  obtained  in  the  analysis  of  petalite  led 
Arfwedson  to  the  discovery  of  lithium  in  1818.    See  pp.  484-90,  49&~7. 


688  DISCOVERY  OF  THE  ELEMENTS 

Unwilling  to  submit  to  this  failure,  Winkler  toiled  incessantly  for 
four  months,  thinking  constantly  of  the  elusive  element  On  February 
6,  1886,  he  filtered  off  the  precipitated  sulfur  as  he  had  done  so  many 
tunes  before  and,  reckless  with  discouragement,  poured  into  the  clear 
filtrate  a  large  quantity  of  hydrochloric  acid.  To  his  great  delight  a  heavy, 
flaky,  white  precipitate  immediately  appeared  (9),  This  substance,  the 
sulfide  of  the  new  element,  dissolved  readily  in  ammonium  hydroxide,  and 
precipitated  again  upon  addition  of  a  large  excess  of  hydrochloric  acid, 
for  it  has  a  most  surprising  property:  it  is  quite  insoluble  in  concentrated 
acids,  yet  readily  soluble  in  water  and  dilute  acids  (7). 

The  new  element,  which  he  called  germanium,  was  isolated  by  heat- 
ing the  dry  sulfide  in  a  current  of  hydrogen.  The  gray,  metallic  powder 
was  found  to  be  less  volatile  than  antimony,  but  the  volatility  of  the 
chloride  explains  why  Winkler  obtained  nothing  but  so'dium  chloride 
when  he  evaporated  the  filtrate  from  the  precipitated  sulfur.  The  ger- 
manium chloride  had  all  been  lost  as  vapor.  The  ore  argyrodite  is  now 
known  to  be  a  double  sulfide  of  silver  and  germanium,  GeS2*4Ag2S. 

Winkler  thought  at  first  that  germanium  was  a  metalloid  like  antimony 
and  arsenic,  and  that  it  would  be  found  to  be  identical  with  Mendeleev's 
predicted  ekastibium,  an  element  which  ought  to  lie  between  antimony 
and  bismuth,  The  scientific  world  immediately  became  interested  in  the 
new  element.  On  February  26th  Mendeleev  contributed  to  the  Berichte 
der  deutschen  chemischen  Gesellscliaft  a  list  of  properties  which  the  new 
element  would  have  to  have  in  order  to  fit  into  the  space  between  antimony 
and  bismuth.  He  thought  it  more  likely,  however,  because  of  the  solubility 
of  the  chloride  in  water  and  because  of  the  white  color  of  the  sulfide,  that 
germanium  was  ekacadmium,  an  element  between  cadmium  and  mercury. 
At  the  same  time  Victor  von  Richter  of  Breslau  wrote  to  Winkler  saying 
he  believed  germanium  to  be  ekasilicon,  the  lowest  homolog  of  tin,  an 
undiscovered  element  between  gallium  and  arsenic.  Two  days  later 
Lothar  Meyer  said  in  the  Berichte  that  he,  too,  believed  germanium  to 
be  the  longed-for  ekasilicon,  and  that  he  had  already  expressed  that 
opinion  to  his  advanced  students  (7). 

Winlder's  months  of  discouragement  were  ended,  and  he  worked 
joyously,  stimulated  by  the  interest  and  encouragement  of  these  eminent 
chemists.  A  vast  amount  of  work  remained  to  be  done,  and  the  obtaining 
of  sufficient  quantities  of  germanium  compounds  became  increasingly 
difficult  Pure  argyrodite  contains  only  7  per  cent  of  germanium,  the 
rich  ore  had  been  exhausted,  and  Winkler  was  obliged  to  work  up  large 
quantities  of  the  low-grade  ore.  He  had  at  first  hoped  to  strike  richer 
deposits  of  argyrodite,  and  had  therefore  been  too  generous  with  hii> 
valuable  germanium  compounds.  Nevertheless,  he  finally  obtained  con- 
vincing proof  that  germanium  is  the  ekasilicon  predicted  by  Mendeleev 


SOME  ELEMENTS  PKEDICTED  BY  MENDELEEV  689 

in  1871.    In  the  following  table  the  predicted  properties  of  ekasilicon  are 
compared  with  the  actual  properties  of  germanium: 

Ekasilicon  Germanium 

(Es)  (Ge) 

Atomic  weight  72  72.32* 

Specific  gravity                                                                       5.5  5.47 

Atomic  volume  13  13.22 

Valence                                                                                    4  4 

Specific  heat                                                                         0.073  0.076 

Specific  gravity  of  dioxide                                                    4.7  4.703 

Molecular  volume  of  dioxide  22  22.16 

Boiling  point  of  tetrachloride                               under  100°  86° 

Specific  volume  of  tetrachlonde                                          1.9  1.887 

Molecular  volume  of  tetrachloride  113  113.35 

Mendeleev  had  made  only  one  mistake  in  his  prophecy.  He  had 
thought  that  ekasilicon,  like  titanium,  would  be  difficult  to  liquefy  and 
volatilize.  Lothar  Meyer,  who  had  disagreed  with  him  on  this  point, 
proved  to  be  correct.  Winkler  afterward  said  that  germanium  contra- 
dicted all  expectations  in  its  occurrence  in  nature.  He  said  that  he  might 
have  expected  to  find  it  combined  with  oxygen  and  accompanied  by 
titanium  and  zirconium  in  rare  Scandinavian  minerals,  but  would  never 
have  thought  to  look  for  it  in  silver  mines  among  the  related  compounds 
of  arsenic  and  antimony  (10). 

Clemens  Winkler  made  brilliant  contributions  both  to  pure  and 
applied  chemistry,  and  had  many  interests  beyond  the  chemical  field. 
Like  H.  Davy  and  A.  G.  Ekeberg,  he  had  poetic  ability,  and  many  of  his 
songs  are  preserved  in  the  songbook  of  the  Freiberg  Academy.  O.  Brirnck 
said  that  these  were  written  in  good  form  and  with  well-chosen  words  (7 ) . 
For  the  entertainment  of  his  guests,  Winkler  often  used  to  write  humorous 
chemical  verses  for  them  to  sing  while  he  played  a  gay  accompaniment 
on  almost  any  instrument  they  might  prefer.  He  resigned  his  professor- 
ship in  1902,  and  died  of  carcinoma  on  October  8,  1904.  His  name  will 
always  be  honored  wherever  true  scientific  greatness  is  appreciated. 

In  1893  the  great  American  mineralogist  and  analytical  chemist 
Samuel  Lewis  Penfield  analyzed  a  mineral  from  Bolivia,  which  he  found 
to  be  identical  in  composition  with  argyrodite,  Ag8GeSQ.  Since  it 
crystallized  in  the  regular  system  whereas  argyrodite  was  then  believed 
to  be  monoclinic,  the  Bolivian  mineral  was  at  first  regarded  as  a  new 
species,  canfieldite.  A.  Weisbach  soon  showed,  however,  that  argyrodite, 
too,  crystallizes  in  the  regular  form.  The  name  canfieldite  was  therefore 
transferred  to  another  kind  of  argyrodite  in  which  some  of  the  germanium 
is  replaced  by  tin  (52,  53,  54). 

*  The  1955  atomic  weight  of  germanium  is  72.60. 


690  DISCOVERY  OF  THE  ELEMENTS 

In  1920  H.  Schneiderhbhn  discovered  a  red  complex  copper  germa- 
nium sulfide  of  uncertain  composition  in  the  Tsumeb  Mine,  Otavi,  South- 
west Africa  (52,  56).  This  mineral,  now  known  as  germanite,  is  an 
important  source  of  germanium  ( 52 ) .  Many  zinc  blendes,  including  those 
of  the  Joplin  (Missouri)  and  Wisconsin  areas,  contain  this  metal,  which 
can  be  enriched  during  the  smelting  process  (39,  52,  55,  57).  L.  M. 
Dennis  and  A.  W.  Laubengayer  of  Cornell  University  showed  in  1926 
that  satisfactory  optical  glass  can  be  made  by  replacing  any  part  of  the 
silica  in  ordinary  glass  with  germanium  dioxide  (58). 

Although  traces  of  germanium  have  been  found  in  many  parts  of 
the  world,  no  mineral  has  been  discovered  in  which  it  is  the  main  con- 
stituent. Most  of  the  ores  which  contain  it  (argyrodite,  canfieldite,  ger- 
manite,  lepidolite,  sphalerite,  and  tourmaline)  are  rare.  In  England, 
coal  flue  dust  is  utilized  as  a  source  of  the  metal.  In  1935  the  flue  dusts 
of  a  zinc  smelter  at  Henryetta,  Oklahoma,  were  found  to  contain  ger- 
manium in  rather  concentrated  form  (35).  No  great  demands  for  it 
arose  until  1942,  when  the  National  Defense  Research  Council  of  the 
United  States  had  need  of  a  very  pure  semi-conducting  metal  for  use  in 
electronic  equipment.  When  it  was  found  that  germanium  has  re- 
markable versatility  in  this  field,  it  acquired  great  commercial  importance 
and  soon  became  five  times  as  valuable  as  gold  (35).  Most  of  the  world 
production  of  germanium  comes  from  the  zinc  ores  of  the  tri-state  district 
(Oklahoma,  Kansas,  and  Missouri),  which  contain  from  0.01  to  0.10  per 
cent  of  it  (35). 

The  remarkable  electrical  property  of  germanium  that  caused  the  un- 
precedented demand  for  it  is  its  ability  to  permit  the  flow  of  electricity 
in  one  direction  and  resist  the  flow  in  the  other  direction.  Although 
vacuum  tubes  are  used  in  the  construction  of  rectifiers  to  convert  alter- 
nating current  to  direct  current,  many  of  them  are  bulky,  fragile,  and 
not  sufficiently  durable,  A  germanium  rectifier  only  a  few  millimeters  in 
diameter  dissipates  no  heat,  reacts  instantly,  and  has  about  ten  times  the 
average  life  of  a  vacuum  tube. 

In  1948,  scientists  of  the  Bell  Telephone  Laboratories  perfected  an 
improved  form  of  the  germanium  rectifier  known  as  a  transistor  (35,  36). 
In  certain  applications  these  transistors  can  compete  successfully  with 
vacuum  tubes.  They  are  already  being  used  in  hearing  aids.  The  semi- 
conductors of  chief  interest  in  transistor  physics  are  germanium  and 
silicon  (36). 


LITERATURE  CITED 

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SOME  ELEMENTS  PREDICTED  BY  MENDELEEV  691 

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692  DISCOVERY  OF  THE  ELEMENTS 

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(56)  ScHNEroERHOHN,  H.,  Uetall  und  Erz,  17,  364  (1920),  Mineralog   Abstr.,  1, 

1589. 

(57)  DENNIS  L.  M.  and  J.  PAPISH,  "Germanium.     I.     Extraction  from  germanium- 

bearing  zinc  oxide/7  J.  Am.  Chem.  Soc.,  43,  2142  (Oct,  1921);  Z.  anorg 
Chem.,  120,  21  (Dec.  14,  1921). 

(58)  DENNIS,  L.  M.,  and  A.  W.  LAUBENGAYER,  "Germanium.     XVII.     Fused  ger- 

manium dioxide  and  some  germanium  glasses,"  /.  Phys  Chem ,  30,  1510-26 
(1926). 

(59)  SJOBEBG,  S.  G.,  "Nils  Gabriel  Sefstrom  and  the  discovery  of  vanadium,"  J. 

Chem.  Educ.,  28,  294-6  (June,  1951). 


Courtesy  E.  R.  Schierz 


The  Gadolin  Medal.  The  Gadolin  Fund  was  established  in  1935 
by  the  Society  of  Finnish  Chemists.  The  first  award  for  this  handsome 
medal  was  made  in  1937  to  Ossian  Aschan  and  Gust.  Komppa.  The 
obverse  bears  a  portrait  of  Johan  Gadolin,  investigator  of  gadolinite; 
the  reverse  side  shows  a  group  of  chemists  studying  the  rare  earths 
from  this  mineral.  See  ref.  (64).  This  picture  of  the  plaster  cast 
of  the  medal,  taken  in  the  studio  of  the  designer,  Emil  Wikstrom, 
was  sent  to  Dr.  Schierz  by  Dr.  E.  S.  Tomula  of  Helsinki. 


The  rare  earths  perplex  us  in  our  researches,  baffle 
us  in  our  speculations,  and  haunt  us  in  our  very 
dreams.  They  stretch,  like  an  unknown  sea  before 
us,  mocking.,  mystifying,  and  murmuring  strange 
revelations  and  possibilities  (1). 


26 

The  rare  earth  elements 


The  rare  earths  are  so  very  much  alike  and  occur  closely  associ- 
ated in  such  complex  minerals  that  it  is  extremely  difficult  to 
separate  them.  They  have  all  been  obtained,  however,  by 
elaborate  and  laborious  fractionation  of  two  mixtures,  the  "yttria" 
of  Gadolin  and  the  "ceria"  of  Klaproth,  Berzelius,  and  Hisinger, 
originally  believed  by  their  discoverers  to  be  pure  oxides.  The 
patient  researches  of  Mosander,  Delafontaine,  Marignac,  Cleve, 
Boisbatidran,  Urbain,  Charles  James,  and  many  others  finally 
resulted  in  the  decomposition  of  the  so-called  "yttria"  into  the 
oxides  now  known  as  yttria,  terbia.,  erbia,  ytterbia,  lutetia,  holmia, 
thulia,  and  dysprosia.  Through  the  persistent  skilful  work  of 
Mosander,  Mangnac,  Boisbaudran,  Brauner,  Auer  von  Welsbach, 
Demar^ay,  Hopkins,  McCoy,  and  others,  the  old  "ceria"  was 
finally  broken  down  into  the  oxides  ceria,  lanthana,  neodymia, 
praseodymia,  samaria,  gadolirtia,  europia,  and  promethium* 
Most  of  the  rare  earth  elements  are  extremely  rare  and  costly 
even  in  the  form  of  their  compounds. 


ich  stores  of  the  rare  earth  minerals  lay  hidden  for  centuries 
in  the  Scandinavian  peninsula  until,  one  day  in  1787S  Lieutenant  Carl  Axel 
Arrhenius  found,  near  the  Ytterby  feldspar  quarry  in  Roslagen,  an  unusual 
black  rock  which  he  at  first  called  ytterite,  but  which  was  later  named 
gadolinite  for  the  famous  Finnish  scientist  Johan  Gadolin  who  detected  in 
it  yttria,  scandia>  and  all  the  rare  earths  of  the  yttria  group. 

In  the  laboratory  of  the  Royal  Mint,  Bengt  Reinhold  Geijer  and 
R  J,  Hjelm  had  taught  Arrhenius  how  to  test  gunpowder  and  had  aroused 
his  interest  in  the  minerals  at  the  School  of  Mines  (22).  On  returrdng 
from  a  visit  to  Paris,  where  he  had  heard  A.-L.  Lavoisier,  C.-L,  Berthollet, 
A.-F.  de  Fourcroy,  and  Guyton  de  Morveau  discuss  the  new  antiphlogistic 
doctrine,  Arrhenius  explained  it  clearly  to  his  Swedish  confreres,  who  had 
hitherto  heard  only  vague  and  distorted  accounts  of  it  (69). 

9  The  discovery  of  promethium  will  be  discussed  in  Chapter  31. 

695 


696  DISCOVERY  OF  THE  ELEMENTS 

The  interruptions  of  army  life  were  never  able  to  stifle  Arrhenius's 
love  of  science,  and  he  always  regretted  "that  he  had  been  snatched  away 
so  early  from  his  studies  and  thrust  into  the  occupations  of  practical  life" 
( 69 ) .  In  the  school  year  1816-17,  when  he  was  about  sixty  years  old,  he 
studied  chemistry  in  Beizelius'  laboratory,  Almost  to  the  close  of  his  life 
he  continued  to  attend  Berzelius'  lectures.  Even  the  disconnected  words 
which  Arrhenius  uttered  during  the  delirium  of  his  last  illness  showed  that 
his  mind  was  still  occupied  with  mmeralogical  chemistry  (69). 

The  first  description  of  gadolinite  was  published  by  Bengt  Reinhold 
Geijer  (1758-1815)  in  Crelfs  Annalen  in  1788.  "I  am  now  sending  you," 
said  he,  "a  specimen  of  a  heavy  stone  which  one  of  my  friends,  Hr.  Lieut. 
Arrhenius,  found.  It  was  discovered  at  Ytterby,  three  miles  from  Stock- 


Johan  Gadolin,  1760-1852.  Professor  of 
chemistry  at  the  University  of  Abo,  Fin- 
land, Discoverer  of  the  complex  earth 
"yttria,"  which  afterward  yielded  an  entire 
series  of  simple  oxides  He  made  a 
thorough  study  of  the  rare  earth  minerals 
from  Ytterby,  Sweden 


holm,  in  the  neighborhood  where  one  gets  quartz  for  the  glassworks.  .  .  . 
It  resembles  asphalt  or  coal"  (22,  74}.  Because  of  its  high  specific  gravity 
it  was  believed  to  contain  tungsten  (wolfram), 

In  1812  Thomas  Thomson  visited  the  Ytterby  quarry.  "It  would  be 
improper,"  said  he,  "while  giving  an  account  of  the  minerals  of  Upland, 
to  pass  by  the  quarry  of  Ytterby,  become  famous  from  the  curious  sub- 
stances that  have  been  found  in  it,  It  lies  rather  less  than  two  English 
miles  north  from  the  fortress  of  Vaxholm,  and  consists  of  a  rock  obviously 
connected  with  gneiss,  that  constitutes  the  basis  o£  the  country;  though 
it  consists  chiefly  of  beautiful  white  felspar,  and  felspar  of  a  flesh  red 


THE  RARE  EARTH  ELEMENTS 


697 


Carl  Axel  Arrhenius,  1757- 
1824.  Swedish  chemist  and 
mineralogist.  In  1787  he  dis- 
covered in  the  Ytterby  quarry 
a  new  black  rock  which  he 
named  ytterbite.  In  1794 
Gadolin  discovered  the  com- 
plex earth  "yttna"  in  this 
mineral,  which  has  since  heen 
renamed  gadolinite 


Courtesy  of  M.  Elisabeth  Parson 


colour.  ...  It  was  in  the  flesh-red  felspar  that  Arrhenius  discovered  the 
black  conchoidal  mineral,  afterwards  distinguished  by  the  name  of 
gadolinite.  Its  specific  gravity  is  above  4.  It  was  analyzed  by  Gadolin 
and  found  by  him  to  contain  a  new  earth,  to  which  the  name  of  Yttria  was 
given,  from  the  appellation  of  the  quarry  where  the  gadoHnite  is  found. 
Probably  the  most  accurate  analysis  of  gadolinite  is  the  last  one  which 
was  made  by  Ekeberg  and  which  I  shall  here  state.  It  was  as  follows: 
yttria,  55.5,  silica,  23.0,  glucina  [beryllia],  4.5;  oxide  of  iron,  16.5;  volatile 
matter,  0.5"  (75). 

Thomson  also  visited  a  quarry  at  Finbo,  about  three  miles  from 
Falun,  where  "specimens  of  gadolinite  have  been  found,  several  of  which 
I  procured  by  the  goodness  of  Assessor  Gahn.  This  mineral,"  said 
Thomson,  "is  very  scarce,  having  been  hitherto  found  only  in  two  places 
of  Sweden:  Ytterby  and  Finbo  and  in  both  places  in  a  rock  belonging 
to  the  species  of  granite.  If  the  same  kind  of  rock  were  properly  examined 
m  other  countries,  there  can  be  little  doubt  that  it  would  be  found.  A 
peculiar  earth  confined  to  a  peculiar  spot,  and  in  very  minute  quantities, 
can  hardly  be  conceived.  Yet  that  is  the  predicament  in  which  three  of 
the  earths  stand  at  present,  namely,  zircoma,  yttria,  and  glucina  [beryllia], 


698  DISCOVERY  OF  THE  ELEMENTS 


Abo,  Finland,  in  1823.    Johan  Gadolin,  the  discoverer  of  the  first  rare  earths, 
was  born  in  Abo,  and  served  there  for  twenty-five  years  as  professor  of 

chemistry. 

while  the  other  six  are  scattered  in  great  profusion  through  the  rocks 
constituting  the  surface  of  the  earth"  (75). 

In  1890  Walfr.  Petersson  published  a  complete  history  of  gadolinite 
and  a  thorough  investigation  of  its  chemical  and  mineralogical  properties, 
His  analyses,  lilce  those  of  F.  A.  Genth  and  C.  W.  Blomstrand,  led  to  the 
formula: 


II  III 


Si2O10  =  Be2FeY2Si2O10     (76}. 


G.  Flink  stated  that  gadolinite  "perhaps  played  a  greater  role  in  the 
history  of  inorganic  chemistry  than  any  other  mineral"  and  that  it  "is 
mainly  found  only  at  two  Scandinavian  localities,  namely  Ytterby  near 
Vaxholm  and  Hittero  near  Flekkefjord  in  Norway.  Other  Scandinavian 
localities  for  it  are  of  little  importance,  and  in  other  countries  it  is  found 
only  as  a  rarity"  (77). 

Johan  Gadolin  was  born  at  Abo  near  Helsingfors  (Helsinki)  on  June 
5,  1760.  His  father,  Jacob  Gadolin,  a  well-known  astronomer  and  physi- 
cist, taught  him  to  love  and  understand  Nature.  After  completing  his 


THE  BAKE  EARTH  ELEMENTS  699 

course  at  the  University  of  Abo,  he  studied  under  Torbern  Bergman  at 
Upsala,  and  acquired  a  broad  education  through  travel  in  Denmark, 
Germany,  Holland,  and  England  (43).  In  1794  Gadohn  investigated  the 
mineral  Lieutenant  Arrhenius  had  discovered  at  Ytterby,  and  found  that 
it  contained  about  38  per  cent  of  a  new  earth.  A.  G.  Ekeberg  soon 
confirmed  the  analysis  (40,  41),  and  mineralogists  aftenvard  named  the 
mineral  gadolinite  in  honor  of  the  Finnish  chemist  (64). 

Gadolin  served  the  University  of  Abo  as  a  professor  of  chemistry  for 
twenty-five  years  (1797-1822),  and  during  this  time  he  made  a  thorough 
study  of  the  wonderful  Ytterby  minerals.  He  also  studied  fluxes  for 
decomposing  iron  ores  for  analytical  purposes,  made  contributions  to 
thermochemistry,  helped  solve  the  questions  of  chemical  proportions  and 
chemical  affinity,  and  published  the  first  Swedish  textbook  that  embraced 
Lavoisier's  views  ( 43 ) . 

He  lived  for  thitry  years  after  his  retirement,  and  died  at  Wirmo, 
Finland,  on  August  15,  1852,  at  the  age  of  ninety-two  years  (65).  In 
1827  the  city  of  Abo  and  the  University  buildings  were  destroyed  by  fire, 
and  Gadolm's  valuable  mineral  collections  were  lost.  The  University  was 
then  transferred  to  Helsingf ors  ( 2 ) , 

YTTRIA  AND  CERIA 

Ekeberg  (40,  41),  M.  H  Klaproth,  and  N.-L  Vauquelin  all  investi- 
gated Gadolm's  new  oxide,  and  it  came  to  be  called  yttria,  a  name  derived 
from  Ytterby,  In  1803  Klaproth  discovered  in  the  mineral  cerite  another 
earth  which  he  called  "terre  ochroite"  but  which  is  now  known  as  ceria* 
Berzehus  and  Wilhelm  Hisinger  also  discovered  ceria  independently,  but 
upon  further  investigation  neither  their  yttna  nor  their  ceria  proved  to 
be  a  pure  oxide  (3). 

LANTHANA  AND  DIDYMIA 

The  proof  of  the  complexity  of  ceria  and  yttria  was  given  by  Carl 
Giistav  Mosander,  one  of  Berzelius*  assistants.  He  was  born  at  Kalmar 
on  September  10,  1797,  was  educated  as  a  pharmacist  and  physician, 
and  served  for  some  time  as  an  army  surgeon  (4),  For  many  years  he 
lived  in  the  same  house  with  Berzelius,  and  his  wife,  who  was  of  Dutch 
ancestry,  helped  Berzelius  to  acquire  a  reading  knowledge  of  that  language 
(5).  When  the  Stockholm  Academy  of  Sciences  moved  into  its  mag- 
nificent new  "palace,"  as  Berzelius  called  it,  Mosander  became  curator 
of  the  mineral  collections,  and  was  given  an  apartment  adjoining  them. 

*  See  Chapter  21,  pp.  551-8. 


700  DISCOVEBY  OF  THE  ELEMENTS 

He  also  had  charge  of  the  chemical  laboratory  for  medical  students  at 
the  Caroline  Institute,  where  he  served  as  professor  of  chemistry  and 

mineralogy  for  many  years, 

He  and  Friedrich  Wohler  often  used  to  go  on  long  tramps  together 
during  the  latter's  memorable  months  at  Stockholm,  and  Mosander  helped 
his  German  friend  prepare  a  valuable  mineral  collection  to  take  back  to 


Carl    Gustav    Mosander,*     1797-1858. 

Swedish  army  surgeon,  chemist,  and 
mineralogist,  Curator  of  the  mineral 
collections  at  the  Stockholm  Academy 
of  Sciences.  Professor  of  chemistry  and 
mineralogy  at  the  Caroline  Institute. 
Discoverer  of  lanthana  and  didymia. 
The  latter  earth  was  afterward  split  by 
Auei  von  Welsbach  into  praseodymia 
and  neodymia 


his  fatherland.  Berzelius'  letters  to  Wohler  contain  frequent  references 
to  Mosander  under  the  affectionate  nickname  "Pater  Moses."  On  October 
12,  1824,  for  example,  Berzelius  wrote: 

Now  here  I  am  alone,  chemicaDy  deserted.  Pater  Moses  is  now  woiking 
for  his  examination,  Hisinger  has  not  yet  returned,  and  Arfvedson,  who  was 
recently  engaged,  is  moored  near  his  fiancee.  .  .  .  However,  my  trine  is 
spent  as  usual  in  a  certain  pleasant  monotony  and  in  moving  back  and  forth 
between  the  writing  desk  and  the  laboratory,  where  I  am  still  busy  with  trifles, 
for  example  with  the  completion  of  the  works  begun  on  the  preparation  of 
lithia,  yttria,  and  zirconia.  .  .  . 

In  November  of  the  same  year  he  wrote  again: 

A  thousand,  thousand  thanks  for  the  interesting  letter  and  for  the  beautiful 
minerals,  which  I  arranged  in  their  proper  places  several  days  ago.  Father 
Moses  thanks  you  no  less  than  do  I.  I  cannot  accustom  myself  to  the  thought 
of  no  longer  finding  Wohler  at  his  desk  in  the  laboratory,  and  even  though  I 

*  Reproduced  from  H  G.  Soderbaum's  "Jac  Berzelius.  Levnadsteckning"  by  kind 
permission  of  Dr  Sbderbaum. 


THE  RARE  EARTH  ELEMENTS 


701 


prefer  to  see  Moses*  face  theie  lather  than  none  at  all,  yet  the  loss  by  the 
deception  is  too  great  .  .  . 

It  may  be  assumed  that  Mosander  passed  his  examinations  successfully, 
for  on  July  15,  1825,  Wohler  wrote  to  his  Swedish  master,  "Moses  heisst 
wohl  jetzt  Hr,  Doctor  Pater  Moses,  wozu  ich  gratulire"*  (6). 

In  1839  Mosander  heated  some  cerium  nitrate  and  treated  the  partly 
decomposed  salt  with  dilute  nitric  acid.  In  the  extract  he  found  a  new 
earth,  which  he  named  lanthana,  meaning  hidden,  meanwhile  retaining 
the  old  name,  ceria,  for  the  oxide  which  is  insoluble  in  dilute  nitric  acid 
(7,  28,  45).  In  the  same  year,  Axel  Erdmann,  one  of  Sef Strom's  students, 
discovered  lanthana  in  a  new  Norwegian  mineral,  which  he  named  mosan- 
drite  in  honor  of  Mosander. 


Johan  August  Arfwedson,t  1792-1841. 
Metallurgist,  chemist,  and  mineralogist. 
The  discoverer  of  lithium.  He  studied 
the  action  of  hydrogen  on  metallic  sul- 
fates,  and  in  1823,  by  heating  the  green 
oxide  of  uranium  in  a  current  of  hydro- 
gen, he  prepared  uranous  oxide,  UOs, 
which  he  believed  to  be  the  metal.  He 
studied  under  Berzelius.  (The  spelling 
Arfvedson  appears  frequently  in  the 
literature.)  See  pp  496-7. 


On  February  1st  Berzelius  wrote  to  Wohler- 

It  is  completely  confirmed.  When  I  showed  ErdmamYs  little  specimen  to 
Mosander,  he  announced  that  he,  too,  had  found  something  new  in  cerite. 
Although  we  see  each  other  every  day,  he  had  never  breathed  a  word  of  it  to 
me,  ...  I  do  not  think  that  during  the  month  when  I  was  ill,  Mosander  did 
any  work  on  his  earth.  I  almost  surmise  that  he  thought,  "Let  Berzelius  worry 
about  it-  I  shall  then  be  free  from  a  lot  of  drudgery."  A  few  days  ago  he  began 
again  At  first  he  let  it  be  understood  that  what  Hisinger  and  I  had  called 
cerium  was  a  mixture  of  two  oxides,  neither  of  which  possessed  the  properties 

*  "Moses  may  now  be  called  Herr  Doctor  Father   Moses,   wherefore  I  offer   con- 
gratulations." 

t  Reproduced  from  H.  G.  Soderbaum's  "Jac.  Berzelius.     Levnadsteckning"  by  land 
permission  of  Dr.  Soderbaum. 


702 


DISCOVERY  OF  THE  ELEMENTS 


of  the  mixture.  ...  I  have  now  studied  pure  eerie  oxide  and  found  that  addi- 
tion of  the  earth  does  not  change  any  of  its  properties.  If  this  were  not  the 
case,  the  discovery  of  the  earth  would  have  occurred  before  Mosander.  .  ,  . 
Mosander  would  not  tell  me  what  he  expects  to  name  his  new  earth.  The 
communications  I  am  now  making  are  for  you  alone.  You  must  not  publish 
anything  about  them.  .  .  . 


.*' 


.{•        /'•-•• 


Edgar  Fahs  Smith  Memorial  Collection., 
University  of  Pennsylvania 

Autograph  Letter  of  C.  G.  Mosander.  His  script  is  almost  illegible,  but 
the  following  is  an  approximate  translation:*  "Stockholm,  Nov.  5S  1841. 
Dear  Brother:  Especially  great  thanks  to  you  for  all  your  trouble  with  my 
specimens.  The  expense  I  have  the  honor  to  include  is  ...  (amount 
illegible),  as  nearly  as  I  can  estimate  it.  The  account  is  enclosed.  Would 
you  please  receipt  it?  Once  again  many  thanks  to  you  for  all  your  trouble. 
Many  greetings  to  Westring.  Respectfully  and  cordially,  C.  G.  Mosander. 

P.  S.     Coarse  filter  paper  costs.  .  ." 

*  The  writer  is  deeply  grateful  to  Miss  Mary  Larson  of  the  Zoology  Department 
at  The  University  of  Kansas  and  to  Mr,  Einar  Bourman  for  the  translation  of  this 
letter  from  the  Swedish  and  for  assistance  in  securing  Swedish  illustrations. 


THE  RARE  EARTH  ELEMENTS 


703 


On  February  12  he  wrote,  "Mosander  seems  willing  to  take  my  sug- 
gestion to  name  it  (the  element)  lanthanum  (lanthan)  and  the  oxide, 
lanthanum  oxide  or  lanthana  (lanthanerde)"  (8). 

Months  passed  by,  and  on  June  18th  Berzelius  wrote  again  to  Wbhler: 

I  can  give  you  no  news  from  Mosander.  For  a  long  time  he  has  not  worked 
at  the  continuation  of  his  experiments,  and  he  no  longer  makes  any  mention  of 
what  he  is  finding,  not  so  much  from  reserve  as  because  he  is  not  doing  any- 
thing; but  he  has  his  mineral-water  establishment  to  manage,  so  that  he  really 
has  very  little  time.  .  .  If  you  write  to  Mosander  yourself,  you  will  probably 
receive  something  from  him  for  the  Annalen 


Didymium  Glass  Goggles. 
A  special  glass  containing 
didymium  is  used  to  protect 
the  eyes  of  the  glass  blower. 
It  transmits  all  light  except  the 
yellow  glare  from  the  hot 
sodium  glass  See  "Goggles 
for  precision  glass  blowing," 
7  Chem.  Educ.,  9,  214  (Feh  , 
1932). 


Courtesy  Central  Scientific  Co 


Wohler  waited  patiently  for  several  months,  and  then  wrote  on 
February  25, 1840,  "The  chemical  world  cannot  understand  why  Mosander 
has  not  yet  published  anything  on  lanthanum."  Two  years  later  Berzelius 
wrote,  "Mosander  still  keeps  working  at  his  lanthanum,  but  says  very 
little  about  it  Meanwhile  I  have  learned  enough  to  know  that  more 
depends  on  it  than  had  been  supposed/* 

On  May  13,  1842,  Berzelius  again  broached  the  subject  to  Mosander. 
To  use  his  own  words: 

I  suggested  to  Father  Moses  that  we  soon  have  a  paper  on  cerium  for  the 
Annalen.  He  laughed  rather  scornfully,  went  down  into  his  laboratory,  for  he 
lives  in  the  house  of  the  Academy,  and  brought  up  a  mortar  half  full  of  a  white, 
slightly  yellowish  powder,  and  asked,  "What  is  that?"  I  admitted  my  igno- 
rance. "That,  Sir,"  he  said,  "is  the  way  eerie  oxide  looks  when  one  has  it  pure 


704  DISCOVERY  OF  THE  ELEMENTS 

It  has  cost  me  a  year's  work  to  get  that  far."  He  added  that  he  was  not  going 
to  publish  any  of  his  results  until  he  had  them  completely  finished.  Although 
he  comes  up  nearly  every  morning  to  chat  with  me  a  while,  and  usually  com- 
plains about  the  difficulties  which  keep  him  from  getting  pure  preparations,  he 
tells  me  nothing  about  his  real  results,  and  I  am  satisfied,  for  it  will  be  all  the 
more  interesting  when  one  gets  them  all  at  once  (9) . 

In  1841  Mosander  had  treated  lanthana  with  dilute  nitric  acid,  and 
had  extracted  from  it  a  new  rose-colored  oxide,  which  he  believed  con- 
tained a  new  element,  He  named  the  new  metal  didymium  because,  as 
he  said,  it  seemed  to  be  "an  inseparable  twin  brother  of  lanthanum"  (27, 
29,46}. 

On  August  30-Sept.  2,  1842,  Berzelius  wrote  Th6ophile-Jules  Pelouze 
concerning  a  meeting  of  Scandinavian  naturalists  which  had  been  held 
in  Stockholm:  "Mr,  Mosander  announced  a  new  metal,  found  with 
lanthanum  in  cerite,  a  metal  which  seems  to  accompany  the  cerium  and 
yttrium  wherever  one  finds  them,  .  .  The  oxide  of  this  metal,  which 
is  brown,  gives  pink  salts;  the  pale  pink  color  of  yttric  and  cerous  salts  is 
due  to  its  presence.  When  the  eerie  oxide  is  entirely  devoid  of  didymium 
oxide  it  has  a  pale  lemon  yellow  color;  yttria  and  lanthanum  oxide  are 
white,  The  didymic  oxide  therefore  imitates  the  cerous  and  lanthanic 
oxides  so  closely  in  its  pioperties  that  there  is  scarcely  any  other  way  of 
separating  these  oxides  except  by  repeated  crystallizations  of  their 
salts.  ,  .  .  This  difficult  separation  of  the  metallic  oxides  present  in  the 
cerite  was  the  reason  why  Mr,  Mosander  delayed  so  long  the  publication 
of  his  expenments  on  lanthanum"  (73).  Pelouze  replied  on  October  19, 
1842:  "Mr.  Mosander  is  a  very  skillful  analyst.  .  .  .  I  appreciate  all  the 
more  the  difficulties  he  overcame,  since  I  spent  three  whole  months  on 
cerite  without  even  suspecting  that  it  had  anything  except  cerium  and 
lanthanum.  I  would  be  greatly  obliged  to  you  if  you  would  send  me  in  a 
letter  a  few  traces  of  didymium  oxide"  (73). 

Wohler  objected  to  this  name  because  Didym,  the  German  form  of 
it,  sounds  rather  childish  and  silly,  "etwas  Kindisches,  etwas  Lappisches." 
Berzelius  replied  in  Mosander's  defense: 

No,  my  dear  friend,  I  have  no  hking  for  this  name,  and  yet  I  do  not  want 
to,  and  cannot,  ask  Mosander  to  change  it,  since  he  has  announced  it  publicly. 
You  surely  do  not  understand  our  friend  Father  Moses.  He  takes  suggestions 
from  no  one.  The  proposal  to  change  a  name  given  by  him  would  be  an  offense 
which  he  would  not  easily  pardon,  and  still  he  would  not  change  it.  H-e  in- 
tentionally looked  for  a  name  beginning  with  D  in  order  to  have  a  symbol  un- 
like those  for  other  metals.  To  be  sure,  it  is  quite  true,  as  you  say,  that  the 
repetition  of  the  same  consonants,  and  of  almost  the  same  vowel  sounds,  has  an 
unpleasant  sound,  but  one  soon  gets  accustomed  to  it,  and  finds  it  endurable, 
and  you  must  do  the  same. 


THE  RARE  EARTH  ELEMENTS 


705 


Berzelius  then  mentioned  a  number  of  accepted  organic  names  which 
sound  much  worse  than  "DidynT  (10).  Didymia  was  regarded  as  a 
pure  earth  until  1885,  when  Auer  von  Welsbach  decomposed  it 

YTTRIA,  ERBIA,  AND  TERBIA 

Having  shown  that  the  earth  originally  called  ceria  was  composed  of 
an  insoluble  portion,  ceria.,  and  a  soluble  portion,  lanihana,  Mosander 
investigated  yttria  in  a  similar  manner  (7).  In  1843  he  showed  that  yttria 
from  which  all  the  ceria,  lanthana,  and  didymia  have  been  removed 
contains  at  least  three  other  earths.  These  are:  a  colorless  oxide,  for 


Marc  Delafontaine.,  1837-1911.  Swiss 
chemist  who  studied  under  J.-G.-G.  de 
Marignac  and  taught  for  a  time  at  the 
University  of  Geneva.  Arriving  in  New 
York  in  1870,  he  followed  the  advice  of 
Louis  Agassiz  and  went  to  teach  in  the 
High  Schools  of  Chicago.  He  also  served 
as  analytical  chemist  and  expert  for  the 
Chicago  Police  Department  in  famous 
criminal  cases,  and  earned  on  research  in 
spectrum  anah  sis 


Courtesy  Mtss  Elizabeth  Parson  and 
Mr.  Jules  Delafontaine 


which  he  kept  the  name  yttria,  a  yellow  earth,  erbia;  and  a  rose-colored 
one,  terbia.  He  separated  them  by  fractional  precipitation  with  ammo- 
nium hydroxide.  Erbia,  the  least  basic  of  the  three,  separated  in  the  first 
fractions,  while  yttria,  the  most  basic  one,  was  found  in  the  last  fractions 

(23). 

Mosander's  work  was  confirmed  by  Marc  Delafontaine,  J.-C.  G.  de 
Marignac,  J.  Lawrence  Smith,  P.  T.  Cleve,  and  Lecoq  de  Boisbaudran, 
but,  for  some  reason,  a  confusing  shift  of  names  occurred.  The  names 
erbia  and  terbia  were  interchanged,  so  that  the  former  now  applies  to 


706 


DISCOVERY  OF  THE  ELEMENTS 


the  rose-colored  oxide  (3)  The  names  of  the  four  elements,  yttrium, 
ytterbium,  erbium,  and  terbium,  have  all  been  derived,  by  the  way,  from 
that  of  the  little  Swedish  town,  Ytterby,  where  the  rare  earth  minerals 
were  first  found. 

Before  closing  this  brief  account  of  Mosander  s  work,  it  seems  fitting 
to  reflect  for  a  moment  over  his  sincere  tribute  to  his  honored  teacher. 
On  April  18, 1848,  he  wrote  regarding  a  translation  of  Berzelius'  textbook: 

My  dear  Wohler:  In  this  case  as  always,  I  follow  the  irresistible  impulse 
of  my  heart  to  say  openly  what  I  believe  to  be  right;  you  may  once  more  test  it, 
and  then  judge,  and  I  am  convinced  that  you  will  appreciate  the  truth  of  what 
I  have  to  say.  The  great  master  will  perhaps  soon  pass  into  another  world,  but 
by  us  and  our  successors  his  name  will  long  be  honored  and  loved,  and  what  he 


T.  Lawrence  Smith,  1818-1883.  Ameri- 
can rmneralogical  and  analytical  chemist 
His  method  of  decomposing  ores  which 
are  to  be  analyzed  for  sodium  and  potas- 
sium is  still  the  standard  procedure  He 
investigated  the  rare  earths  m  samarskite 
and  verified  Mosander's  conclusions  re- 
garding the  complex  nature  of  yttria. 


Edgar  Fahs  Smith  Memorial  Collection, 
University  of  Pennsylvania 

has  accomplished  here— that  you  know  as  well  as  I  do— was  not  done  for  the  sake 
of  vainglory,  but  out  of  pure  zeal  for  truth  and  enlightenment,  and  the  motive 
for  his  researches  has  always  sprung  from  a  pure  source,  then  shall  the  right  of 
defending  Science  and  himself,  ere  his  life  is  extinguished,  be  denied  him  in  the 
last  moment  when  he  could  devote  his  undiminished  mental  powers  to  the 
service  of  Science?  Impossible.  .  .  .  Literal  translation  or  none  (II). 

Berzehus  died  at  Stockholm  on  August  7,  1848.  His  mind  remained 
clear  until  the  end,  but  during  the  last  six  days  he  lay  half  asleep,  and 
spoke  no  more.  Mosander  died  ten  years  later,  on  October  15,  1858,  at 
Angsholm  near  Drottningholm  (4). 


THE  RARE  EARTH  ELEMENTS 


707 


Portrait  of  Berzelius  from  a  daguerreo- 
type taken  m  Berlin  in  1845,  three  years 
before  his  death* 


Betty  Berzelius  nee  Poppius  (Baroness 
Berzelius  ),t  1811-1884.  Daughter  of 
state  councilor,  G.  Poppius.  When  she 
married  Berzelius  in  1835  he  was  al- 
ready a  man  of  great  renown,  and  the 
baronetcy  was  conferred  on  him  at  the 
wedding  See  Chapter  XI,  p  315 


*  Reproduced  from  H.  G.  Soderbaum's  "Jac.  Berzelius.     Levnadsteckning"  by  kind 
permission  of  Dr.  Sdderbaum, 

t  Reproduced  from  H.  G.  Soderbaum's  "Jac'  Berzelius.     Levnadsteckning"  by  kind 
permission  of  Dr.  Sdderbaum. 


708 


DISCOVERY  OF  THE  ELEMENTS 


ERBIA,  YTTERBIA,  AND  SCANDIA 

In  1878  the  Swiss  chemist  Marignac  discovered  that  erbia  contained 
a  new  earth  which  he  called  yUerbia  (21).  Jean-Charles  Galissard  de 
Marignac,  a  descendant  of  a  Huguenot  family  that  had  fled  from 
Languedoc  early  in  the  eighteenth  century,  was  born  in  Geneva  on  April 
24,  1817.  When  he  was  sixteen  years  old,  he  entered  the  Ecole  Poly- 
technique  at  Paris,  He  also  spent  two  profitable  years  at  the  School  of 
Mines,  and  then  rounded  off  his  education  by  traveling  through  Scandi- 
navia and  Germany.  In  1840  he  went  to  Giessen  to  study  under  Justus 
von  Liebig,  but,  in  spite  of  the  latter's  influence,  he  preferred  inorganic 
chemistry  to  organic. 


Jean-Charles  Galissard  de  Marignac, 
1817-1894.  Swiss  chemist  who  discov- 
ered ytterbia  and  gadolima  and  made 
many  important  contributions  to  the 
chemistry  of  the  rare  earths.  Professor 
of  chemistry  at  the  University  of  Geneva. 
He  made  precise  determinations  of  the 
atomic  weights  of  many  elements,  and 
by  separating  tantalic  and  columbic 
(niobic)  acids,  proved  that  tantalum  and 
columbium  (niobium)  are  not  identical. 


Marignac's  life  work,  which,  like  that  of  Stas,  consisted  in  making 
many  precise  determinations  of  atomic  weights  in  order  to  test  William 
Prout's  hypothesis  (71),  won  BerzehW  sincerest  praise,  for  he  wrote: 

I  place  the  highest  value  on  your  experiments  concerning  atomic  weights. 
The  patience  with  which  you  repeat  each  experiment  a  large  number  of  times, 
the  sagacity  with  which  you  vary  your  methods,  making  use  only  of  those  which 
can  give  reliable  results,  and  the  conscientious  manner  in  which  you  give  the 
numbers  dictated  by  the  balance  ought  to  assure  for  you  the  complete  confi- 
dence of  chemists  (44) . 

After  working  for  a  time  at  the  Sevres  porcelain  works,  Marignac 
returned  to  Switzerland  to  accept  a  modest  position  as  professor  of 


THE  RARE  EARTH  ELEMENTS     709 

chemistry  at  the  Geneva  Academy.  From  1845  to  1878  he  taught  both 
chemistry  and  mineralogy,  and  carried  on  his  researches  in  a  damp,  dark 
cellar.  During  the  last  ten  years  of  his  life,  he  lay  prostrate,  suffering 
intensely  from  a  disease  of  the  heart,  from  which  death  finally  brought 
release  on  April  15,  1894  (12). 


P,  T.  Cleve,  1840-1905.     Swedish  chem- 
ist, geologist,  botanist,  and  hydrographei 
Professor  of  chemistry  at  Upsala.     Dis- 
coverer of  thulium  and  independent  dis- 
coverer of  holmium 


He  began  his  study  of  the  rare  earths  in  1840,  when  he  was  barely 
twenty-three  years  old.  According  to  P.  T.  Cleve,  "Marignac's  work  on 
the  rare  earths  is  undoubtedly  the  most  important  in  this  particular  depart- 
ment of  chemistry"  (13).  In  1878  Marignac  heated  some  erbium  nitrate 
from  gadolinite  until  it  decomposed.  When  he  extracted  the  resulting 
mass  with  water,  he  obtained  two  oxides:  a  red  one,  for  which  he 
retained  the  name  erbia,  and  a  colorless  one,  which  he  named  ytterbia 
(13,  42,  57),  In  the  following  year  L.  K  Nilson  isolated  the  earth 
scandia*  the  oxide  of  Mendeleev's  predicted  ekaboron,  from  ytterbia. 

ERBIA,  HOLMIA,  AND  THULIA 

The  erbia  left  after  the  removal  of  ytterbia  and  scandia  was  still 
further  resolved  by  Per  Teodor  Cleve,  f  who  was  born  on  February  10, 

*  See  Chapter  25,  pp.  677-83 

t  For  additional  biographical  notes  on  Cleve,  see  /.  Chem.  Educ  ,  7,  2698  (Nov.,  1930). 


710 


DISCOVERY  OF  THE  ELEMENTS 


1840.  He  was  the  thirteenth  child  of  a  Stockholm  merchant.  After  grad- 
uating from  the  University  of  Upsala  in  1863,  he  studied  for  a  time  in 
C.-A.  Wurtz's  laboratory  in  Paris,  and  in  1874  he  became  a  professor  at 
Upsala.  True  lover  of  Nature  that  he  was,  he  could  never  confine  his 
activities  closely  to  one  branch  of  science,  but  was  interested  alike  in 
chemistry,  geology,  botany,  and  hydrography.  He  wrote  his  scientific 
papers  in  a  lucid,  pleasing  style,  and  also  produced  literature  of  esthetic 
value  (14). 


Interior  Court  of  a  German  Baker's  House.*    Berzelius'  laboratory  at  the  right. 


Cleve's  fame  rests  chiefly,  however,  on  his  discoveries  among  the 
rare  earths.  After  obtaining  some  erbia  from  which,  all  the  ytterbia  and 
scandia  had  been  removed,  and  after  noticing  that  the  atomic  weight  of 
the  erbium  was  not  constant,  he  succeeded  in  resolving  the  earth  into  three 
constituents:  erbia,  holmia,  and  thulia  (21).  The  absorption  bands  of 
holmium  had  already  been  noticed  by  the  Swiss  chemists  M.  Delafontaine 

*  Reproduced  from  H.  G.  Soderbatan's  "Jac-  Berzelius.     Levnadsteckning"  by  kind 
permission  of  Dr.  Soderbaum. 


THE  RARE  EARTH  ELEMENTS 


711 


and  J.-L.  Soret  (1827-1890),  who  had  announced  the  existence  of  an 
'element  X,"  later  found  to  be  identical  with  Cleve's  holmium  (35). 
Louis  Soret  was  a  professor  of  physics  at  the  University  of  Geneva 
He  studied  the  laws  of  electrolysis,  defined  the  conditions  for  the  pro- 
duction of  ozone  and  determined  its  density  and  chemical  constitution; 
devised  ingenious  optical  instruments;  and  was  the  first  scientist  to  make 
actinometnc  measurements  on  the  summit  of  Mont  Blanc  (67).  In  1878 
he  recognized  the  presence  of  a  new  "earth  X"  in  erbia  and  characterized 
it  by  its  absorption  spectrum,  but  later  accepted  the  name  holmia  which 
Cleve  gave  it  (67).  He  died  in  Geneva  in  1890  at  the  age  of  sixty- three 


Jons     Jacob     Berzelius.*     1779-1848. 

(From  a  painting  by  J,  Way.)  Ber- 
zelius  was  an  independent  discoverer  of 
the  earth  "ceria"  and  much  of  the  early 
research  on  the  rare  earths  was  done  in 
his  laboratory 


years.  Since  Cleve  was  an  independent  discoverer  of  the  element  holmium, 
his  name  for  it  has  been  accepted  by  chemists  ( 14,  36,  67 ) .  Holmium  was 
named  for  Cleve's  native  city,  and  the  word  thulium  is* derived  from  Thule, 
an  old  name  for  Scandinavia. 

In  spite  of  his  devotion  to  organic  and  inorganic  chemistry,  Cleve 
never  lost  interest  in  biology.  During  his  later  years  he  made  an  extended 
study  of  the  plankton  of  Skagerak  and  the  North  Sea,  especially  of  the 
freshwater  algae  and  diatoms,  in  order  to  locate  the  ocean  currents. 

Although  he  found  little  time  to  mingle  with  his  colleagues,  he  enjoyed 
an  occasional  happy,  social  evening  with  his  family  and  friends.  Hans 
and  Astrid  Euler  said  of  him,  "His  merry  irony  played  upon  all  those  for 

*  Reproduced  from  H.  G.  Sdderbaum's  "Jac.  Berzelius  Levnadstecking"  by  kind 
permission  of  Dr.  Soderbaum. 


712 


DISCOVERY  OF  THE  ELEMENTS 


whom  unyielding  principles  and  passionateness  caused  unnecessary  trou- 
ble, and  upon  scientific  pedantry  no  less  than  upon  religious  and  social 
prejudice;  he  himself  was  liberal  in  the  broadest  sense  of  the  word,  and 
unyielding  only  in  his  rectitude."  He  retired  from  teaching  at  the  age 
of  sixty-five  years,  hoping  to  devote  the  rest  of  his  life  to  the  study  of 
plankton.  He  died  a  few  months  later,  however,  on  June  18,  1905,  after 
severe  suffering  with  pleuritis  (14). 

SAMARIA  AND  GADOLINIA 

Marignac  believed  as  early  as  1853  that  Mosander's  didymia  was  not 
a  pure  substance,  and  later  spectroscopic  work  of  Marc  Delafontaine  and 
of  Lecoq  de  Boisbaudran  indicated  that  the  spectrum  of  didymia  varied 
according  to  its  source.  Boisbaudran  in  1879  added  ammonium  hydroxide 
to  a  solution  of  it?  and  noticed  that  another  earth  precipitated  before  the 
didymia.  Since  the  spectrum  of  this  new  oxide  was  found  to  be  different 


A  Reconstruction  of  BerzehW  Birthplace  at  Wafversunda  ( Vaversunda ) , 
Sweden,  showing  the  buildings  as  they  appeared  in  his  time.* 

from  that  of  didymia,  Boisbaudran  concluded  that  it  must  be  a  new 
earth,  which  he  named  samaria  (26,  27).  In  1886  he  obtained  from  it 
still  another  earth,  which,  however,  proved  to  be  identical  with  the  sub- 

*  Reproduced  from  H.  G.  Soderbaum's  "Jac,  Berzelius.  Levnadstecloiing"  by  kind 
permission  of  Dr.  Soderbaum. 


THE  RABE  EARTH  ELEMENTS 


13 


stance  which  Marignac  had  separated  from  samarskite  in  1880,  and  to 
which  he  had  given  the  provisional  name  Ya  (3),  With  Marignac's 
assent,  BoLsbaudran  named  this  oxide  gadolinia  (34,  57).  Both  these 
earths  were  named  for  minerals  in  which  they  occur,  samarskite  and 
gadolinite. 

NEODYMIA  AND  PRASEODYMIA 

Marignac,  Lecoq  de  Boisbaudran,  Cleve,  and  Bohuslav  Brauner  all 
believed  didymium  to  be  a  mixture  of  elements,  but  none  ot  them  were 
able  to  make  the  difficult  separation  (49).  In  1882  Professor  Brauner  of 
the  University  of  Prague  examined  some  of  his  didymia  fractions  with 
the  spectroscope  and  found  a  group  of  absorption  bands  in  the  blue  region 
( A—449-443 )  and  another  in  the  yellow  ( A=590-568 )  ( 53,  66 ) ,  *  These 
two  groups  of  bands  are  now  known  to  belong  to  two  earths,  praseodymia 
and  neodymia,  respectively.,  which  Baron  Auer  von  Welsbach  obtained 
in  1885  by  splitting  didymia  (3,  30,  32,  58). 


The   Caroline   Institute   of  Medicine   and   Surgery    at 
Stockholm.    Both  Berzelms  and  Mosander  taught  chem- 
istry at  this  School  of  Medicine. 


Carl  Auer,  Baron  von  Welsbach,  was  born  on  September  1,  18587  at 
Vienna  (4).  After  completing  the  courses  at  the  gymnasium  and  Poly- 
technicum  of  his  native  city,  he  went  to  Heidelberg  to  study  under  Robert 
Bunsen.  The  quiet,  industrious,  unsociable  boy  from  Austria  soon  became 
a  favorite  of  the  great  German  master.  Auer  was  deeply  interested  in 
inorganic  chemistry,  and  especially  in  minerals.  The  rare  earth  minerals 
of  the  north  attracted  him  so  much  that  he  began  to  search  for  specimens. 

*  See  p.  717. 


714 


DISCOVERY  OF  THE  ELEMENTS 


Although  the  first  little  collection  that  he  showed  to  Bunsen  would  not 
have  filled  a  child's  hand,  Bunsen  laughingly  told  him  to  begin  his  investi- 
gation (16).  Carl  Auer  s  researches  on  the  rare  earths,  which  were  begun 
in  this  modest  manner  at  Heidelberg,  were  continued  for  the  rest  of  his 

life. 

On  June  18,  1885,  he  announced  to  the  Vienna  Academy  of  Sciences 
that  by  repeated  fractionation  of  ammonium  didymiurn  nitrate  he  had 
succeeded  in  splitting  didymia  into  two  earths,  for  which  he  proposed 
the  names  praseodymia  and  neodymia,  green  didymia  and  new  didymia. 
Many  chemists  were  skeptical,  and  he  afterward  said,  "Only  Bunsen,  to 


Herbert  Newby  McCoy,  1870-1945.  Amei- 
ican  chemist  who  made  outstanding  contri- 
butions to  radioactivity  and  the  chemistry  of 
the  lare  earths  In  1904  he  showed  that 
ladmm  is  produced  by  spontaneous  trans- 
mutation of  uranium  Three  years  later,  in 
collaboration  with  W.  H.  Ross,  he  pointed 
out  the  identical  chemical  behavior  of  the 
compounds  of  certain  elements  which  F 
Soddy  later  called  isotopes.  Dr  McCoy 
also  gave  the  first  quantitative  proof  that 
the  a-ray  activity  of  uranium  compounds  is 
directly  proportional  to  their  uranium  con- 
tent (78), 


Courtesy  Dr    Ethel  M    Terry 
(Mrs.  H    N    McCoy) 


whom  I  fiist  showed  the  discovery,  recognized  immediately  that  a  splitting 
of  didymium  had  actually  been  accomplished.  This  acknowledgment 
from  Bunsen,  who  had,  as  is  known,  published  very  beautiful  and  com- 
prehensive researches  on  didymium,  showed  how  unselfishly  this  great 
investigator  used  to  judge  the  researches  of  younger  men"  (16). 
Neodymia  and  praseodymia  have  never  been  decomposed  into  simpler 
oxides. 

Baron  Auer  is  best  remembered  for  his  invention  of  the  incandescent 
gas  mantle,  a  truly  great  advance  in  the  history  of  illumination  (55). 
Instead  of  attempting  to  produce  a  gas  which  would  burn  with  a  luminous 
flame,  he  decided  to  use  a  non-luminous  flame  to  heat  a  refractory  mantle 
to  incandescence.  The  problem,  as  he  said,  "was  not  to  find  a  process 
by  which  an  infusible  compound  could  be  given  a  definite  shape.  This 
invention  is  founded,  above  all,  on  the  fact,  proved  by  numerous  experi- 


THE  RARE  EARTH  ELEMENTS 


715 


ments,  that  molecular  mixtures  of  certain  oxides  aie  possessed  of  properties 
which  cannot  be  deduced  from  those  of  their  constituents."  One  of  the 
engineers  to  whom  he  explained  his  plans  said,  "In  my  works  we  only  take 
notice  of  serious  ideas." 

After  many  discouragements  Baron  von  Welsbach  finally  impregnated 
the  fabric  for  the  mantles  in  a  mixture  containing  one  thousand  grams 
of  thorium  nitrate,  ten  grams  of  cerium  nitrate,  five  grains  of  beryllium 
nitrate,  1.5  grams  of  magnesium  nitrate,  and  two  thousand  grams  of 
water  ( IS ) .  His  first  patent  for  the  incandescent  lamp,  known  in  Germany 
as  the  "Auerlicht"  and  in  America  as  the  Welsbach  mantle,  was  dated 
September  23,  1885. 


Baron    Auer    von    Welsbach,    1858-1929. 

Austrian  chemist  and  chemical  technologist. 
Discoverer  of  praseodymium  and  neo- 
dymium.  Inventor  of  the  Welsbach  gas 
mantle,  the  osmium  filament  electric  lamp, 
and  the  automatic  gas  lighter. 


Baron  Auer  chose  as  his  motto  the  appropriate  words  "more  light" 
but  preferred  to  write  it  "plus  lucis"  as  a  reminder  of  his  early  struggles 
with  Latin  (49).  In  1901  Kaiser  Franz  Josef  elevated  him  to  the  he- 
reditary nobility  with  the  title  of  Freiherr  von  Welsbach.  When  the 
Kaiser  remarked,  "You  have  had,  so  I  hear,  considerable  success  with 
your  discoveries,"  Baron  von  Welsbach  quickly  replied,  "Yes,  Your  Maj- 
esty, up  to  the  present  more  than  40,000  people  throughout  the  entire 
world  have  found  employment  through  my  discoveries/'  This  reply  left 
Franz  Josef  speechless  (16). 

Auer  von  Welsbach  also  invented  the  automatic  gas  Lighter  based  on 
a  pyrophoric  alloy  of  iron  and  cerium,  and  the  osmium-filament  electric 


716 


DISCOVERY  OF  THE  ELEMENTS 


lamp  (54),  the  first  successful  electric-light  bulb  with  a  metallic  filament, 
which,  however,  was  soon  supeiseded  by  the  tungsten  and  tantalum  lamps. 
His  home,  Welsbach  Castle,  commanded  a  glorious  view  of  the  Carin- 
thian  Alps,  and  his  chief  lecieations  were  hunting,  fishing,  and  gardening. 
In  the  park  were  many  exotic  plants,  including  cedars  from  Lebanon,  that 
he  had  carefully  nurtured  until  they  could  withstand  the  severe  climatic 
conditions  at  the  high  altitude  of  800  meters.  On  the  ground  floor  of 
the  castle  there  was  a  well-equipped  laboratory  containing  a  valuable 


Bohuslav  Brauner,  1855-1935 

Professoi  of  chemistry  at  the 
Bohemian  University  of 
Prague  He  made  brilliant 
contributions  to  analytical 
chemistry,  the  determination 
of  atomic  weights,  and  the 
chemistry  of  the  rare  earths 
In  1902  he  predicted  the  ex- 
istence of  element  61,  now 
known  as  prome thrum 


J    HetfTOVsky,  Czechoslov    Chem, 
Communications 


spectroscope  which  his  aunt  had  provided  for  his  early  researches,  a 
library  of  valuable  books  with  uncut  pages,  which  had  belonged  to  Bunsen, 
and  an  unsurpassed  collection  of  rare  earths.  These  treasures  were  care- 
fully guarded  by  the  ever-faithful  "Buzi,"  a  terrier  who  allowed  no  one 
but  his  master  to  touch  even  a  piece  of  paper.  On  August  2,  1929,  Baron 
Auer  was  seized  with  severe  abdominal  pain.  After  a  painful  examina- 
tion by  physicians,  who  realized  the  serious  nature  of  the  illness,  "he  got 
up,  went  into  the  garden,  looked  around,  closed  up  his  study,  burned 
a  few  papers,  stood  for  a  long  time  before  his  fathers  portrait,  then  went 
into  the  laboratory,  covered  his  spectroscope,  stroked  it  tenderly  with  his 
hand,  glanced  at  the  other  things,  took  leave  of  his  last  unfinished  thulium 


THE  HARE  EARTH  ELEMEN'IS  717 

series  with  a  motion  of  the  hand,  closed  the  rooms  again,  and  quietly  lay 
down"  (49).    Twelve  hours  later  he  entered  into  eternal  rest 

The  following  literal  translation  of  a  postcard  from  Professor  Bohuslav 
Brauner  to  Dr.  Max  Speter  is  published  by  kind  permission  of  Dr.  Speter. 
It  was  written  in  reply  to  a  question  as  to  whether  or  not  Brauner  and 
Auer  von  Welsbach  were  students  under  Mendeleev.  Dr.  Brauner  was 
about  seventy-eight  years  old  when  he  wrote  this  card. 

Prague,  Weinberge,  Polska  14, 

May  18,  1933 
ESTEEMED  COLLEAGUE: 

It  pleased  me  that  you  welcomed  iny  reprints  1  am  a  genuine  Praguer.  I 
was  with  Master  Mendelejew  in  1882,  but  did  not  hear  that  he  [Auer  von 
Welsbach]  had  been  with  him.  M.  wished  to  work  with  me,  on  H2.O  in  fact, 
yet  I  could  not  remainl  M.  visited  me  in  Prague,  and  I  later  went  to  see  him 
in  Petersburg.  I  remember  well  that  you  once  visited  me  in  Prague  It  is  in- 
teresting that  A.  W.  [Auer  von  Welsbach]  often  did  the  same  as  I.  I  learned 
from  Bunsen  in  1878-9  how  to  work  with  the  rare  earths,  he  did  the  same  in 
1883,  but  when  I  was  visiting  the  same  place,  he  [A.  v.  W.?]  did  not  present 
himself.  I  found  in  1882,  through  study  of  the  decomposition  products  of  the 
old  didymium,  that  it  can  be  split  into  two  earths  (absorption  spectra)  and 
published  a  note  on  it  in  the  Wiener  Anzelger.  He  published  his  work  on 
praseodymium  and  neodyimum  in  1885. 

Cordially  vours, 

PROF.  BR  \UNEH 


HOLMIA  AND  DYSPROSIA 

In  the  year  1886  Lecoq  de  Boisbaudran  separated  pure  holmia  into 
two  earths,  which  he  called  holmia  and  dysprosia.  He  accomplished  this 
by  fractional  precipitation,  first  with  ammonium  hydroxide  and  then  with 
a  saturated  solution  of  potassium  sulfate,  and  found  that  the  constituents 
of  impure  holmium  solutions  precipitate  in  the  following  order:  terbium, 
dysprosium,  holmium,  and  erbium  (3,  37,  48).  Lecoq  de  Boisbaudran 
never  had  an  abundant  supply  of  raw  materials  for  his  remarkable 
researches  on  the  rare  earths,  and  he  once  confided  to  Professor  Urbain 
that  most  of  his  fractionations  had  been  carried  out  on  the  marble  slab 
of  his  fireplace  (56). 

SAMARIA  AND  EUROPIA 

Eugene-Anatole  Demargay,  the  discoverer  of  europium,  was  born 
in  Paris  on  New  Year's  Day,  1852.  He  studied  at  the  Lycee  Condorcet, 
spent  a  year  in  England,  and  at  the  age  of  eighteen  years  entered  the 


718 


DISCOVERY  OF  THE  ELEMENTS 


Ecole  Polytechnique  (4).  He  was  interested  not  only  in  chemistry,  but 
also  in  geology,  natural  histoiy,  and  languages.  His  good  humor,  intel- 
lectual integrity,  and  ability  to  think  independently  soon  won  the  respect 
and  friendship  of  his  professors,  A.-A.-T.  Cahours,  C.-A.  Wurtz,  H,  Sainte- 
Claire  Deville,  J.-B.-A.  Dumas,  Charles  Friedel,  M.-A.  Cornu,  Paul 
Schutzenberger,  and  Lecoq  de  Boisbaudran,  and  his  love  of  pure  science 
brought  him  into  contact  with  many  younger  investigators,  including 
Henri  Moissan,  A.-H.  Becquerel,  and  the  Curies.  After  serving  for  some 
time  as  Cahours'  assistant  at  the  Ecole  Polytechnique,  he  gave  up  his 
position  in  order  to  travel  through  Algeria,  Egypt,  and  India  ( 50 ) .  When 
he  returned  to  Pans,  he  devoted  all  his  time  to  research  in  pure  science 


Eugene-Anatole     Demar<?ay,     1852-1904. 

French  chemist  who  discovered  the  ele- 
ment europium  and  gave  spectroscopic 
proof  of  the  discovery  of  radium  by  M 
and  Mme,  Curie.  He  investigated  many 
terpenes  and  ethers,  and  studied  the  vola- 
tility of  metals  at  low  temperatures  and 
pressures 


His  first  investigations,  begun  in  1876,  were  in  organic  chemistry. 
His  study  of  the  Cs  terpenes  and  the  ethers  of  the  unsaturated  acids 
proved  to  be  of  practical  value  in  the  perfume  industry.  While  studying 
the  sulfides  of  nitrogen  he  suffered  a  serious  accident.  The  explosion  of 
a  cast-iron  vessel  completely  destroyed  one  of  his  eyes,  yet,  after  recover- 
ing from  the  injury  and  shock,  he  continued  his  dangerous  researches  on 
compressed  gases.  In  his  famous  laboratory  on  the  Boulevard  Berthier 
he  had  the  finest  apparatus  for  producing  vacua  to  be  found  in  Paris. 
This  was  used  tor  studying  the  volatility  of  zinc,  cadmium,  and  gold  at 
low  temperatures  and  pressures  ( 50 ) . 


Berzelius'  Grave*  in  the  Solna  Churchyard 


In  order  to  study  the  effect  of  very  high  temperatures  on  spark 
spectra,  Demarcay  constructed  an  induction  coil  with  a  short  secondary 
wire  of  large  diameter,  which  gave  intensely  hot,  luminous,  globular 
sparks.  By  using  electrodes  of  very  pure  platinum,  he  was  able  to 
eliminate  from  the  spectrum  of  the  substance  he  wished  to  examine  all 
foreign  spectra  except  the  well-known  lines  of  platinum.  This  was  the 
apparatus  with  which  he  studied  the  spectra  of  the  rare  earths. 

In  1901  Demargay  made  an  elaborate  series  of  fractionations  of 
samarium  magnesium  nitrate  which  resulted  in  the  discovery  of  a  new 
earth,  europia  (3,  31,  59).  Since  he  could  read  a  complex  spectrum  "Tike 
an  open  book,"  he  was  frequently  called  upon  to  pass  judgment  on 
supposedly  new  elements,  and  was  the  first  to  observe  the  new  lines 
of  radium  in  some  barium  salts  brought  by  Pierre  Curie. 

Had  he  been  granted  a  longer  life,  Dema^ay  might  have  made  a 
more  thorough  study  of  the  compounds  of  europium,  but  in  1904  death 

*  Reproduced  from  H.  G.  Soderbaum's  "Jac.  Berzelrus.    Levnadsteckning"  by  courtesy 
of  Dr.  Soderbaum. 


720  DISCOVERY    OF   THE  ELEMENTS 

brought  an  end  to  his  researches.  Although  he  had  realized  for  some  tirne 
that  his  life  would  soon  be  cut  short,  he  nevertheless  felt  grateful  for 
the  years  he  had  lived"  and  "asked  for  no  further  reward  than  that  felt 
by  a  keen  intelligence  when  it  gives  rise  to  a  flash  of  thought  that  will 
be  remembered  throughout  the  world"  (50), 

YTTERBIA  AND  LUTETIA 

In  1907  Georges  Urbain  separated  ytterbia  into  two  constituents. 
By  repeated  fractional  crystallization  of  ytterbium  nitrate  from  nitric 
acid  solution,  he  obtained  two  oxides  with  different  properties.  One  of 
these  he  named  neoytterbia  in  order,  as  he  said,  "to  leave  to  the  illustrious 


Georges  Urbain,  1872-1938.  French 
chemist,  painter,  sculptor,  and  musician. 
President  of  the  Societe  de  Chimie  and 
of  the  International  Committee  on  Atomic 
Weights.  His  enthusiasm  for  research 
was  acquired  from  Pierre  Curie  and 
Charles  FriedeL  See  ref.  (70) 


Courtesy  Dr  R.  E    Oesper 


Marignac,  in  the  future,  the  credit  of  his  fundamental  discovery"  (52). 
The  other  oxide  he  called  lutecia  from  an  old  name  for  his  native  city, 
Paris  (3,  38,  39,  51).  The  spelling  has  been  changed  to  lutetia.  The 
element  he  named  neoytterbium  is  now  known  simply  as  ytterbium. 
Although  these  elements  were  found  to  be  identical  with  the  "alde- 
baranmm"  and  "cassiopeium"  discovered  independently  by  Auer  von 
Welsbach  at  about  the  same  time,  Urbain's  names  for  them  have  been 
widely  accepted.* 

*  In  German  periodicals,  however,  lutetmm  is  called  cassiopeium. 


THE  RARE  EARTH  ELEMENTS  721 


Courtesy  Tenney  L    Datvi 

Memorial  Plaque  Designed  by  Georges  Urbain  in  Honor  of  the  Schiitzen- 
berger  Centennial.  This  is  a  fine  example  of  Professor  Urbain's  artistic  ability, 

Georges  Urbain  was  born  on  April  12,  1872,  received  his  doctorate 
from  the  University  of  Paris  in  1899,  and  afterward  became  a  professor 
there  (4).  He  received  inspiration  and  encouragement  in  his  researches 
from  Pierre  Curie  and  Lecoq  de  Boisbaudran  (53).  Until  his  death  on 
November  5,  1938,  he  was  a  professor  at  the  Sorbonne  and  chief  of  the 
chemical  division  of  the  French  Institute  of  Physico-Chemical  Biology 
founded  by  Baron  Edmond  de  Rothschild  (17).  Professor  Urbain  was 
a  member  of  the  Institute  of  France  and  of  the  International  Commission 
on  Atomic  Weights.  He  is  famous  not  only  for  his  work  on  the  rare 
earths  (52),  spectroscopy,  magnetism,  cathode  phosphorescence,  and 
atomic  weights,  but  also  for  his  beautiful  artistic  productions,  among 
which  may  be  mentioned  the  plaque  which  he  designed  in  honor  of  the 
Schiitzenberger  centennial  (18,  70). 

Before  the  news  of  Urbain's  discovery  reached  America,  Professor 
Charles  James  of  the  University  of  New  Hampshire  had  prepared  a 
large  amount  of  very  pure  lutetia.  Although  deeply  disappointed  because 
his  caution  and  delay  in  publishing  his  results  had  caused  him  to  lose 
priority  in  this  discovery,  he  accepted  Urbain's  results  without  question 
and  never  pushed  his  own  claim  (19,  60). 

Charles  James  was  born  at  Earls  Barton,  near  Northampton,  England, 
on  April  27,  1880.  At  the  age  of  nineteen  years  he  entered  University 


722  DISCOVERY  OF  THE  ELEMENTS 

College,  London,  where  Sir  William  Ramsay  and  his  colleagues  had 
recently  discovered  the  inert  gases.  From  1906  until  his  untimely  death 
in  1928,  Professor  James  served  as  an  inspiring  teacher  of  chemistry  at 
the  University  of  New  Hampshire.  He  published  in  the  Journal  of  the 
American  Chemical  Society  about  sixty  papers  on  the  rare  earth  elements, 
worked  out  processes  for  extracting  them  from  their  minerals  and  separat- 
ing them  one  from  another,  made  accurate  determinations  of  their  atomic 
weights,  and  discovered  new  rare  earth  compounds.  He  often  prepared 
these  substances  in  unusually  large  amounts  and  generously  shared  them 
with  other  investigators  (60). 

Professor  James  displayed  remarkable  ingenuity  in  devising  new, 
economical,  efficient  methods  of  separating  the  rare  earths  and  in  observ- 
ing the  progress  of  these  separations  by  photographing  the  spectra  of 
his  products.  After  thorough  study  of  the  solubilities  of  the  rare  earth 
bromates,  he  worked  out  a  bromate  method  of  fractionating  the  members 
of  the  cerium  group.  The  James  method  of  fractional  crystallization  of 
the  double  magnesium  rare  earth  nitrates  is  probably  the  most  widely 
used  means  of  separating  this  group  into  fractions  (60). 

Although  it  is  extremely  difficult  to  prepare  rare  earth  salts  pure 
enough  for  atomic  weight  determinations,  the  James  values  for  thulium, 
samarium,  and  yttrium  agree  almost  exactly  with  the  atomic  weights 
accepted  by  the  International  Committee.  Professor  James  also  made 
outstanding  contributions  to  the  chemistry  of  other  rare  elements  such 
as  scandium,  gallium,  germanium,  beryllium,  and  uranium  (60). 

This  remarkable  work  was  all  accomplished  during  a  very  short  span 
of  life.  Professor  James  died  in  Boston  on  December  10,  1928,  at  the 
age  of  forty-eight  years.  In  the  following  year,  a  fine,  new,  four-story 
chemistry  building  at  the  University  of  New  Hampshire  was  named  in 
his  honor  (19). 

The  following  diagrams  which  Professor  James  prepared  for  the 
Fourteenth  Edition  of  the  Encyclopedia  Britannica  show  very  clearly  the 
separations  by  which  the  original  complex  earths  "ceria"  and  "yttria"  were 
resolved  into  the  simple  oxides  of  the  rare  earth  metals. 


(Y 
Y<Er...Tb 


^Element  61,  then  known  as  illinium  (II),  is  now  called  promethium  (Pm). 


THE  RARE  EARTH  ELEMENTS  723 


Courtesy  of  University  of  New  Hampshire 


Charles  James,  1880-1928.     Director  of  the  chemistry  department  at  the 

University  of  New  Hampshire.    Author  of  many  papers  on  the  rare  earths. 

Independent  discoverer  of  lutetium.     He  was  born  in  England  and  studied 

under  Sir  William  Ramsay. 


724  DISCOVERY  OF  THE  ELEMENTS 


B.  Smith  Hopkins,  Professor  of  Chemistry 

at  the  University  of  Illinois.     He  carried 

out  many  researches  in  the  fields  of  rare 

earths  and  atomic  weights. 


The  metals  of  the  rare  earths  comprise  the  largest  of  all  the  natural 
groups  (25,  47).  Most  of  them  have  been  prepared  in  the  metallic  state 
(20,24,33,  61,  62,63,68). 


LITERATURE  CITED 

( 1 )  BASKEHVILUE,  C.,  "The  elements:    Verified  and  unverified/'  Science  [N.  S.]  19, 

93  (Jan.  15,  1904).    Quotation  from  Sir  William  Crookes. 

( 2 )  T.  E.  T.,  "Johan  Gadolin,"  Nature,  86,  48-9  ( Mar.  9,  1911 ). 

( 3 )  SPENCER,  J.  F.,  "The  Metals  of  the  Rare  Earths,"  Longmans,  Green  and  Co., 

London,  1919,  pp.  2-10. 

(4}  POGGENDORFF,  J.  C.,  "Biographisch-Literarisches  Handworterbuch  zur  Ge- 
schichte  der  exakten  Wissenschaften,"  6  vols.,  Verlag  Chemie,  Leipzig  and 
Berlin,  1863-1937.  Articles  on  Mosander,  Auer  (von  Welsbach),  Demar- 
Qay,  Urbain,  and  Gadolin. 

(5)  SODERBAUM,  H.  G.,  "Jac.  Berzelius  Bref,"  Vol.  2,  part  5,  Almqvist  and  Wiksells, 

Upsala,  1912-1914,  p.  43.    Letter  of  Berzelius  to  Mulder,  Sept.  24,  1837. 

(6)  WALLACH,  O.,  "Briefwechsel  zwischen  J.  Berzelius  und  F.  Wohler,"  Vol.   1, 

Verlag  von  Wilhelm  Engelmann,  Leipzig,  1901,  p.  57. 

(7)  "Latanium,  a  new  metal,"  Phil  Mag.,  14,  390-1  (May,  1839);  Pogg.  Ann.,  46, 

648  (1839). 

(8)  WALLACH,  O.,  "Briefwechsel  zwischen  J.  Berzelius  und  F.  Wohler,"  Ref.  (6), 

Vol.  2,  p.  94. 


THE  RARE  EARTH  ELEMENTS     725 

(9)  Ibid.,  Vol.  2,  pp.  295-6. 

(10)  Ibid.,  Vol.  2,  pp.  320-1. 

(11)  Hid.,  Vol.  2,  p.  718. 

(12)  ADOR,  E.,  "Jean^Charles  Galissard  de  Marignac,  Sein  Leben  und  seine  Werke," 

Ber.,  27,  979-1021  (Part  4,  1894). 

(13)  "Chemical  Society  Memorial  Lectures,  1893-1900,"  Gurney  and  Jackson,  Lon- 

don, 1901,  pp.  468-89.    Marignac  Memorial  Lecture  by  Cleve. 

(14)  EULER,  H.  and  A.  EULER,  "Per  Theodor  Cleve/*  Ber.,  38,  4221-38  (Part  4, 

1905);  Kungl.  Svenska  Vetenskapsakademiens  Arsbok,  1906,  pp.  187-217. 

(15)  AUER  VON  WELSBACH,  CARL,  "History  of  the  invention  of  incandescent  gas- 

lighting,"  Chem.  News,  85,  254-6  (May  30,  1902). 

(16)  FELDHAUS,  "Zum  70.    Geburtstage  von  Auer  von  Welsbach,"  Chem.-Ztg.,  52, 

689-90  (Sept.  1,  1928). 

(17)  KHOUVINE,  Y.,  "The  New  French  Institute  of  Physico-Chemical  Biology,"  /. 

Chem.  Educ.,  7, 1053-4  (May,  1930). 

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903  (Apr.  19,  1880), 


726  DISCOVERY   OF   THE   ELEMENTS 

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Letter  of  Berzelius  to  Marignac,  May  31,  1844. 

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Kersten  of  Freiberg,"  Phil  Mag.  [3],  15,  286-7  (Oct.,  1839). 

(46)  MOSANDER,  C.  G.,  "On  the  new  metals  lanthanrum  and  didymium,  which  are 

associated  with  cerium;  and  on  erbium  and  terbium,  new  metals  associated 
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(47)  FRIEND,  J.  N.,  "The  periodic  sphere  and  the  position  of  the  rare  earth  metals/* 

Chem.  News,  130,  196-7  (Mar.,  1925);  J.  Chem.  Educ.,  2,  409-11  (May, 
1925). 

(48)  DE  BOISBAUDRAN,  LECOQ,  "Sur  le  dysprosium,"  Compt.  rend,,  102,   1005-6 

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(49)  D'ANS,  J.,  "Carl  Freiherr  Auer  von  Welsbach,"  Ber.,  64,  59-92  (May  6,  1931). 

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ytterbium,"  Chem.  News,  96,  271-2  (Dec.  6,  1907);  "Lutecium  and  neo- 
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(52)  URBAIN,  G.,  "Twenty-five  years  of  research  on  the  yttrium  earths/'  Chem.  Re- 

views, 1,  143-85  (July,  1924). 

(53)  URBAIN,  G.s  "Discours  sur  les  Elements  Chimiques  et  les  Atomes.     Hommage 

au  Professor  Bohuslav  Brauner,"  Rec.  trav.  chim.  Pays-Bas,  44,  281-304 
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(54)  "Karl  Auer,  Bitter  von  Welsbach,"  /.  Chem.  Educ.,  6,  2051-2  (Nov.,  1929). 

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(56)  URBAIN,  G.,  "Lecoq  de  Boisbaudran,"  Chem-Ztg.,  36,  929-33  (Aug.  15,  1912). 

(57)  ADOR,  E.,  "Oeuvres  completes  de  J.-C.  G.  de  Marignac,"  Vol.  2,  Masson  et  Cie., 

Paris,  pp.  683-711. 

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THE  RARE  EARTH  ELEMENTS  727 

(60)  SMITH,  MELVIN  M.,  L.  A.  PRATT,  and  B.  S.  HOPKINS,  "The  Life  and  Work  of 

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231,  138-71  (1937). 

(63)  BERTRAND,  L.,  "Metallic  europium,"  La  Nature,  66,  92  (Aug.  1,  1938). 

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Sealed  Tube  Containing  Iodine  iso- 
lated by  Courtois  from  the  mother 
liquors  from  the  preparation  of  salt- 
peter. This  tube,  belonging  to  the 
Solvay  Company  of  Belgium,  was  pre- 
sented at  the  iodine  centenary  (Nov. 
9,  1913)  through  the  courtesy  of  M. 
C.  Crinon. 


From  Toraude's  "Bernard  Courtois  et  la 
Decouverte  de  I'lode" 


La  recherche  d'un  corps  simple  est  toujours  tres  captivante  (1,  17). 
The  search  for  an  element  is  always  captivating. 

La  science  ne  par  ait  pas  settlement  avoir  pour  mission  de  satisfaire  chez 
rhomme  ce  besoin  de  tout  connaitre,  de  tout  apprendre,  qui  caracterise 
la  plus  noble  de  nos  facultes;  elle  en  a  aussi  une  autre,  moins  brillante 
sans  doute,  mais  peut-etre  plus  morale,  je  dirai  presque  plus  sainte,  qui 
consiste  a  coordonner  les  -forces  de  la  nature  pour  augmenter  la  produc- 
tion et  rapprocher  les  hommes  de  I'egalite  par  Yuniversalite  du  bien- 
etre  (2). 

Science  appears  to  have  as  its  mission  not  merely  the  satisfaction  of 
mans  need  of  learning  and  understanding  everything,  which  charac- 
terizes the  noblest  of  our  faculties;  it  has  another  aim,  doubtless  less 
brilliant  but  perhaps  more  moral,  I  would  almost  say  more  sacred, 
which  consists  in  coordinating  the  forces  of  nature  to  increase  produc- 
tion and  make  men  more  nearly  equal  by  the  universality  of  comfort. 


27 

The  halogen  family 


The  discovery  of  the  four  halogens  required  a  little  more  than  a 
century.  Although  Scheele  prepared  chlorine  in  1774  by  the 
action  of  manganese  dioxide  on  hydrochloric  acid,  it  was  be- 
lieved to  be  a  compound  until  after  1810,  when  Sir  Humphry 
Davy  gave  convincing  proof  of  its  elementary  nature.  In  1811 
Bernard  Courtois  isolated  iodine  from  the  mother  liquor  obtained 
by  leaching  the  ashes  of  marine  algae.  Balard's  discovery  of 
bromine  fifteen  years  later  was  an  especially  important  event  in 
the  history  of  science,  for  chemists  were  just  beginning  to  realize 
that  there  are  family  groups  among  the  elements  and  Dobereiner 
soon  observed  that  chlorine,  bromine,  and  iodine  form  a  closely 
related  triad.  The  long,  dangerous  search  for  fluorine,  which 
brought  suffering  and  death  to  several  promising  chemists,  cul- 
minated successfully  in  1886  through  the  brilliant  efforts  of 
Moissan. 


CHLORINE 


-n  his  famous  research  on  pyrolusite,  C.  W.  Scheele  allowed 
hydrochloric  acid,  or  spiritus  sails  as  he  called  it,  to  stand  in  contact  with 
finely  ground  pyrolusite  (crude  manganese  dioxide),  and  noticed  that 
the  acid  acquired  thereby  a  suffocating  odor  like  that  of  warm  aqua 
regia,  and  "most  oppressive  to  the  lungs."  He  thought  that  the  manganese 
dioxide  had  taken  the  combustible  principle,  phlogiston,  from  the  hydro- 
chloric acid,  and  therefore  called  the  gas  "dephlogisticated  marine  acid" 
or  "dephlogisticated  muriatic  acid"  He  noticed  that  it  dissolved  slightly 
in  water,  imparting  to  it  an  acid  taste,  that  it  bleached  colored  flowers 
and  green  leaves,  and  that  it  attacked  all  metals  (3). 

A.-L.  Lavoisier  thought  that  all  acids  contain  oxygen.  Dr.  William 
Henry,  who  obtained  hydrogen  by  passing  an  electric  discharge  through 
gaseous  "marine  acid,"  concluded  that  it  came  from  the  water,  and  that 
water  must  be  an  essential  constituent  of  hydrochloric  acid  (37,  38}. 
C.-L.  Berthollet,  who  was  a  partisan  of  Lavoisier  and  not  a  phlogistonist, 
noticed  that  calcined  pyrolusite,  which  had  lost  some  of  the  oxygen  from 
its  manganese  dioxide,  yielded  less  of  the  suffocating  gas,  "dephlogisticated 

729 


730 


DISCOVERY  OF  THE  ELEMENTS 


marine  acid,"  than  could  be  obtained  from  an  equal  weight  of  fresh 
pyrolusite.     He  concluded  that: 

It  is  therefore  to  the  vital  air  [oxygen]  of  the  manganese  [pyrolusite],  which 
combines  with  the  marine  acid,  that  the  formation  of  the  dephlogisticated 
marine  acid  is  due.  I  ought  to  state  that  this  theory  was  presented  and  an- 
nounced some  time  ago  by  M.  Lavoisier,  and  that  M.  de  Fourcroy  made  use  of 
it  in  his  "Elements  of  Chemistry  and  Natural  History"  to  explain  the  properties 
of  dephlogisticated  marine  acid  such  as  they  were  then  known. 


Count  Claude-Louis  Berthollet,  1748- 
1822.  French  chemist  and  physician. 
Professor  at  the  £cole  Normale.  He  col- 
laborated with  Lavoisier  in  his  researches 
and  in  reforming  chemical  nomenclature. 
Berthollet's  "Essai  de  statique  chimique" 
emphasized  the  importance  of  the  relative 
masses  of  the  reacting  substances  in 
chemical  reactions. 


\ 


Berthollet  thought  that  the  gas  now  known  as  chlorine  was  a  loose 
compound  of  hydrochloric  acid  and  oxygen  (11-2),  or,  to  use  his  own 
words,  that: 

[Dephlogisticated  marine  acid]  is  manifestly  formed  by  the  combination 
of  vital  air  with  marine  acids  but  in  it  the  vital  air  is  deprived  of  a  part  of  the 
principle  of  elasticity,  and  adheres  so  feebly  to  the  marine  acids  that  the  action 
of  light  suffices  to  disengage  it  promptly,  light  having  more  affinity  for  its  base 
than  marine  acid  has  (4) . 

In  the  year  1807  Sir  Humphry  Davy  obtained  hydrogen  by  the 
action  of  potassium  on  "muriatic  acid,"  and  concluded  that  it  must  have 
come  from  the  water  in  the  acid,  and  that  the  oxygen  in  the  water  must 
have  converted  the  potassium  to  potassium  oxide  (5).  Gay-Lussac  and 
Thenard,  however,  did  not  accept  the  explanation.  They  argued  that 
the  hydrogen  came  neither  from  the  acid  nor  from  the  water,  but  from 


THE   HALOGEN   FAMILY 


731 


William  Henry,  1775-1836.  British  chemist 
and  manufacturer,  and  author  of  books  on 
chemistry.  He  discovered  that  when  a  gas  is 
absorbed  in  a  liquid,  the  weight  dissolved  is 
proportional  to  the  pressure  of  the  gas  ( Henry's 
law).  He  thought  that  water  was  an  essential 
constituent  of  hydrochloric  acid. 


Title  Page  of  William  Henry's 
"Epitome  of  Chemistry."     In 

the    original,    Benjamin    Silli- 
man's  autograph  can  be  seen 
just  above  the  words  "Profes- 
sor of  Chemistry." 


CHEMISTR  Y, 


THHEE  PARTS. 


PART  I, 


PART  II, 

.   FOR   THE  AUAi'VSis   OF    WtKERAL  WATK&S  }  Of 


FART  lit 

Hf5TRflCTI0»*    F««t    ArfLVlttd    iHKXICAl,  TESTS 


WIU4AM  I3LENEY. 


t'ROMTHE  FOURtH  ENOUSH  EDITION  t 

JJOC8  K 


732  DISCOVERY  OF  THE  ELEMENTS 

the  potassium,  which  was  thereupon  changed  back  into  caustic  potash, 
which  then  reacted  with  the  acid.  They  tested  the  "oxidized  marine 
acid"  (chlorine)  with  glowing  charcoal,  but,  since  they  could  detect  no 
oxygen  they  concluded  that  oxygen  was  formed  only  in  the  presence  of 
water.  All  their  attempts  to  decompose  the  chlorine  by  heating  it  with 
dry  charcoal  proved  fruitless  (6). 

L.-J.  Gay-Lussac  and  L.-J.  Thenard  believed  ( 1 )  that  muriatic  gas 
contains  one-fourth  of  its  weight  of  water,  (2)  that  oxymuriatic  gas  is 
a  compound  of  oxygen  and  some  other  substance,  and  (3)  that  the  sub- 
stance obtained  by  heating  calomel  with  phosphorus  is  a  triple  compound 


Sir  Humphry  Davy,  1778-1829.  British 
chemist  who  isolated  the  alkali  and 
alkaline  earth  metals  and  boron,  and 
proved  that  chlorine  is  an  element.  Gay- 
Lussac  and  Thenard  isolated  boron  in- 
dependently at  about  the  same  time. 


consisting  of  dry  muriatic  acid,  oxygen,  and  phosphorus.  Davy's  final 
views  on  these  three  points  were  as  follows:  (1)  muriatic  acid  is  com- 
posed of  oxymuriatic  acid  (chlorine)  and  hydrogen,  (2)  chlorine  is  an 
element,  and  (3)  the  substance  obtained  by  heating  calomel  with  phos- 
phorus is  a  compound  of  the  elements  chlorine  and  phosphorus. 

Since  Berthollet,  Gay-Lussac,  Thenard,  A.-F.  de  Fourcroy,  and  J.- 
A.-C.  Chaptal  all  belonged  to  the  French  school  founded  by  the  illustrious 
Lavoisier,  it  was  difficult  for  them  to  admit  the  existence  of  an  acid  that 
contained  no  oxygen,  but  nevertheless  they  soon  had  to  yield  to  the 
convincing  evidence  presented  by  Sir  Humphry  (8,  41).  Dr.  John 
Murray  in  Edinburgh  and  Berzelius  in  Stockholm  continued,  however, 
for  some  time  to  regard  chlorine  as  a  compound. 


THE  HALOGEN   FAMILY 


733 


After  iodine  was  discovered  in  1811,  the  evidence  for  the  elementary 
nature  of  chlorine  became  still  more  convincing,  and  by  1820  even 
Berzelius  had  yielded  (9).  When  Anna,  his  cook,  remarked  one  day 
that  the  flask  she  was  washing  smelled  of  "oxidized  muriatic  acid," 
Berzelius  replied,  "Anna,  you  mustn't  speak  of  oxidized  muriatic  acid  any 
more;  from  now  on  you  must  say  chlorine"  (10). 

The  discovery  of  bromine  by  A.-J.  Balard  and  the  preparation  of 
prussic  (hydrocyanic)  acid,  an  oxygen-free  acid,  by  Gay-Lussac  made 
the  evidence  conclusive.  Davy's  formal  announcement  of  the  elementary 


Jons  Jacob  Berzelius,*    1779-1848.      He 

was  one  of  the  last  chemical  authorities 

to  be  convinced  of  the  elementary  nature 

of  chlorine. 


nature  of  chlorine  was  made  in  a  memoir  which  he  read  before  the  Royal 
Society  on  November  15,  1810  (8). 

Sir  Humphry  Davy's  life  was  a  short  one,  and  his  last  years  were 
marred  by  continued  illness.  In  a  letter  written  in  Rome  in  February, 
1829,  he  said,  "If  I  die,  I  hope  that  I  have  done  my  duty  and  that  my 
life  has  not  been  vain  and  useless"  (50).  Three  weeks  later  he  was 
stricken  with  palsy,  from  which  he  never  recovered.  Even  the  devotion 
and  medical  skill  of  his  younger  brother,  Dr.  John  Davy,  were  in  vain. 

*  Reproduced  from  H.   G.  Soderbaum's  "Ja,c.  Berzelius  Levnadsteckning"  by  kind 
permission  of  Dr.  Soderbaum. 


734 


DISCOVERY  OF  THE  ELEMENTS 


When  spring  came,  Dr.  Davy  thought  it  best  to  take  his  brother  from 
Rome  to  Geneva  in  order  to  avoid  the  hot  Italian  summer.  The  long 
journey  by  horse  and  carriage  was  most  exhausting,  and  Sir  Humphry 
died  at  Geneva  on  May  29,  1829.  His  desire  that  his  life  might  be  useful 
was  so  richly  fulfilled  that  his  name  will  always  be  honored  as  that  of 
a  supremely  great  scientist  and  humanitarian. 

Bleaching  toith  Chlorine.  In  1785  Count  C.-L.  Berthollet  noticed 
that  an  aqueous  solution  of  chlorine  destroys  vegetable  colors  just  as  the 
gas  itself  does  (119).  In  the  following  year  he  used  it  successfully  in 
bleaching,  and  communicated  his  results  to  scientists  and  technical  men, 


Anna  Sundstrom,*  Berzelius'  House- 
keeper. She  kept  house  for  him  for 
many  years  before  he  was  married  and 
prepared  the  meals  in  the  kitchen-lab- 
oratory, where  his  sand  bath  on  the 
stove  was  never  allowed  to  cool. 
Berzelius  once  said  that  he  could  not 
have  thus  entrusted  the  management 
of  his  home  to  any  other  person  of  the 
servant  class. 


including  James  Watt.  "Mr.  Watt  of  Birmingham/'  said  William  Henry, 
".  .  ,  was  the  first  person  in  this  country  [England]  to  carry  the  discovery 
into  effect,  by  bleaching  several  hundred  pieces  of  linen  by  the  new 
process,  at  the  works  of  a  relative  near  Glasgow"  (120}.  After  Watt  had 
tried  out  the  process  on  1500  yards  of  linen  in  the  bleach-fields  of  his 
father-in-law  near  Glasgow,  Professor  Copeland  introduced  it  to  the 
bleachers  of  Aberdeen,  and  Dr.  Thomas  Henry,  father  of  William  Henry, 
began  bleaching  operations  at  Manchester  (120,  121,  122}. 

In  the  early  processes  developed  in  England,  France,  Germany,  and 
Austria,  the  bleaching  agent  was  chlorine  gas  or  chlorine  water.  To 
prevent  its  injurious  effects  on  the  respiratory  system,  workmen  used  to 

*  Reproduced  from  H.  G.  Soderbaum's  "Jac.  Berzelius.  Levnadsteckning"  by  kind 
permission  of  Dr.  Soderbaum. 


THE   HALOGEN   FAMILY  735 

protect  their  faces  with  handkerchiefs  moistened  with  dilute  alkali 
(123).  Berthollet  found,  however,  that  the  addition  of  alkali  to  the 
bleaching  liquor  deprived  it  of  its  disagreeable,  suffocating  odor  without 
impairing  its  bleaching  power.  A  solution  of  chlorine  in  potash  was 
sold  under  the  name  of  Javelle  water  (123).  Hypochlorite  solutions, 
however,  do  not  keep  well  (124). 

As  early  as  1788,  Thomas  Henry  prepared  a  bleaching  liquor  from 
lime  and  chlorine,  and  it  became  a  common  practice  among  bleachers  to 
economize  by  substituting  lime  for  the  more  expensive  pearlash  from  wood 
ashes  (123).  In  1795  the  Hungarian  botanist  and  chemist  Paul  Kitaibel 
distilled  a  mixture  of  salt,  pyrolusite,  and  sulfuric  acid,  and  passed  the 
liberated  chlorine  ("oxygenated  acid  of  salt")  into  limewater.  He  made 
many  experiments  with  solid  bleaching  powder,  and  used  it  to  bleach 
textiles  and  wax  (125). 

Charles  Tennant  of  Glasgow,  who  was  then  engaged  in  bleaching  at 
Darnley,  prepared  solid  bleaching  powder  in  1798  and  was  granted  a 
patent  for  it  early  in  the  following  year.  He  originally  prepared  it  by 
heating  a  mixture  of  salt,  pyrolusite,  and  sulfuric  acid  in  a  leaden  still 
and  absorbing  the  liberated  chlorine  in  sifted  slaked  lime  in  a  leaden 
receiver  (124).  J.  Lawrence  Smith  regarded  this  as  "the  greatest  ad- 
vancement since  the  discovery  of  chlorine  towards  rendering  it  available 
in  the  arts,  for  it  can  now  be  transported  readily  to  all  parts  of  the  world, 
and,  moreover,  we  are  indebted  to  this  form  (so  to  speak)  of  chlorine 
for  the  discovery  and  manufacture  of  that  great  boon  to  suffering  hu- 
manity, viz.,  chloroform"  (121).  The  discovery  of  bleaching  powder 
also  stimulated  the  growth  of  cotton  and  saved  for  agricultural  purposes 
thousands  of  acres  of  arable  land  which  had  formerly  been  used  as  green- 
swards for  the  slow  bleaching  of  textiles  by  the  oxygen  of  the  air.  Chlo- 
rine," said  J.  Lawrence  Smith,  "has  revolutionized  this,  and  a  few  hours 
accomplishes  that  which  formerly  required  days;  and  a  few  hundred 
square  feet  containing  properly  constructed  vats  takes  the  place  of 
thousands  of  acres  of  land"  (121). 

Disinfecting  with  Chlorine.  A  reviewer  in  the  Medical  Repository 
wrote  in  1802  concerning  Guyton  de  Morveau's  "Treatise  on  the  means  of 
purifying  infected  air,  of  preventing  contagion,  and  arresting  its  progress" 
that  "The  most  powerful  and  efficacious  anti-contagious  agent  which  he 
knows  is  the  oxygenated  muriatic  acid  gas  [chlorine].  The  process  for 
preparing  this  differs  from  the  ordinary  muriatic  [hydrochloric]  acid  gas 
already  mentioned,  only  by  the  addition  of  a  small  quantity  of  black  oxyd 
of  manganese  ...  in  powder"  (126).  This  anonymous  reviewer  (possibly 
Samuel  Latham  Mitchill,  editor  of  the  Medical  Repository)  questioned 
the  conclusions  of  Guyton  de  Morveau  and  believed  that  aqueous  solu- 
tions of  potash,  soda,  soap,  and  lime  were  more  efficacious  (126). 


736      DISCOVERY  OF  THE  ELEMENTS 

Chlorine  in  the  Human  Body.  Chlorine  enters  into  the  composition 
of  all  secretions  and  excretions  of  the  human  body,  and  gastric  digestion 
takes  place  in  a  medium  containing  hydrochloric  acid  (127). 


IODINE* 

Iodine,  one  of  the  most  beautiful  of  all  the  elements,  was  first  ob- 
served in  1811  by  Bernard  Courtois,  who  was  born  on  February  8,  1777, 


C  E 

From  Toraude's  ""Bernard  Courtois  et  la  Decouv&rte  de  VIode" 
The  Old  Dijon  Academy  (B)  and  the  Birthplace  (E)  of  Bernard  Courtois 

(present  condition  of  the  buildings).  In  the  middle  of  the  nineteenth 
century  the  latter  building  was  enlarged  and  made  higher.  The  street  at  G 
is  the  Rue  Monge  ( formerly  Rue  du  Pont  Arnauld ) .  When  it  was  widened, 
the  quarters  in  the  Academy  Building  formerly  occupied  by  Bernard's  father, 
Jean-Baptiste  Courtois,  assistant  to  Guyton  de  Morveau,  were  torn  down. 


in  a  house  just  across  the  street  from  the  famous  old  Dijon  Academy.  His 
father,  Jean-Baptiste  Courtois,  was  a  saltpeter  manufacturer  who  used 

*  The  pictures  of  the  Dijon  Academy,  the  sealed  tube  containing  the  first  iodine,  and 
the  Courtois  autograph  letter  have  been  reproduced  by  courtesy  of  Dr.  L.-G.  Toraude 
from  his  book,  "Bernard  Courtois  et  la  Decouverte  de  Tlode."  The  autograph  letter 
belongs  to  the  departmental  archives  of  the  Cote  d'Or.  The  photograph  of  the 
sealed  tube  was  taken  at  Dijon  on  Nov.  9,  1913,  the  day  of  the  ceremony  in  honor 
of  the  one  hundredth  anniversary  of  the  discovery  of  iodine. 


THE   HALOGEN    FAMILY  737 


From  Toraude's  "Bernard  Courtois  et  la  Decouverte  de  I'lode" 

Autograph  of  Bernard  Courtois  (1794).  Translation:  "I  have  received 
from  D'orgeu  township  50  casks  of  saltpeter  solution  which  they  have  drawn 
from  their  property  and  which  they  have  asked  me  to  take  because  they 
have  no  one  sufficiently  trained  to  extract  the  saltpeter  from  it.  Dijon  the 
llth  of  Messidor,  the  2nd  year  of  the  Republic,  one  and  indivisible.  B. 
Courtois,  son  ____  "  He  was  seventeen  years  old  when  he  wrote  this  receipt. 


to  assist  Guyton  de  Morveau,  the  lawyer,  in  his  brilliant  lectures  on  chem- 
istry. Thus  the  son  lived  constantly  in  a  chemical  environment,  dividing 
his  time  between  the  paternal  saltpeter  works  and  the  laboratories  of 

the  Academy. 

After  Citizen  Guyton  was  called  to  the  Legislative  Assembly  in  1791, 
J.-B.  Courtois  gave  up  his  position  at  the  Academy  in  order  to  devote 
all  his  time  to  the  manufacture  of  niter.  After  assisting  his  father  for 
a  time,  Bernard  was  apprenticed  for  three  years  to  a  pharmacist  at 
Auxerre,  M.  Fremy,  the  grandfather  of  Edmond  Fremy,  the  famous 
chemist.  In  the  meantime  Guyton  de  Morveau  had  become  the  director 
of  the  ficole  Polytechnique,  and  through  his  intervention  Bernard  Cour- 
tois was  admitted  to  the  laboratories  of  this  school  to  study  under  Four- 
croy.  Here  Courtois  entered  into  his  research  and  courses  in  pure 
chemistry  with  pleasure  and  enthusiasm.  In  1799,  however,  he  was  called 
to  serve  his  country  as  a  pharmacist  in  the  military  hospitals.  In  1804, 
while  serving  as  preparateur  under  Armand  Seguin,  he  made  an  important 
investigation  of  opium  (51). 


738  DISCOVERY  OF  THE  ELEMENTS 

Although  J.-B.  Courtois  failed  in  business,  he  was  an  honest  man,  and 
both  father  and  son  struggled  hard  to  pay  their  creditors.  In  1808  Ber- 
nard Courtois  married  Madeleine  Eulalie  Morand,  a  young  girl  of  humble 
parentage  who  could  barely  read  and  write. 

Along  the  coasts  of  Normandy  and  Brittany  many  plants  live  at 
shallow  depth  in  the  ocean,  and  some  of  them  are  cast  ashore  by  the  waves 
and  tides.  For  plants  such  as  these  the  French  writers  of  the  early  nine- 
teenth century  used  the  term  varech,*  from  which  the  English  words 
wrack  and  wreck  have  been  derived  (13).  By  burning  Fucus,  Laminar ia, 
and  other  brown  algae  gathered  at  low  tide,  and  by  extracting  the  ash 
with  water.  Courtois  obtained  some  mother  liquors  known  as  salin  de 
varech,  or  soude  de  uarech. 

The  algae  that  Courtois  used  yield  an  ash  containing  chlorides, 
bromide,  iodides,  carbonates,  and  sulfates  of  sodium,  potassium,  magne- 
sium, and  calcium.  In  his  day,  however,  they  were  valued  merely  for 
their  sodium  and  potassium  compounds,  which  were  recovered  by 
burning  the  dried  algae  in  longitudinal  ditches  along  the  seashore  and 
leaching  the  ashes  at  the  works. 

As  evaporation  proceeded,  sodium  chloride  began  to  precipitate  and 
later  potassium  chloride  and  potassium  sulfate.  The  mother  liquor  then 
contained  the  iodides  of  sodium  and  postassium,  part  of  the  sodium  chlo- 
ride, sodium  sulfate,  sodium  carbonate,  cyanides,  polysulfides,  and  some 
sulfites  and  hyposulfites  resulting  from  the  reduction  of  sulfates  during 
calcination. 

To  destroy  these  sulfur  compounds  Courtois  added  sulfuric  acid,  and 
on  one  eventful  day  in  1811  he  must  have  added  it  in  excess  (54) .  To  his 
astonishment  lovely  clouds  of  violet  vapor  arose,  and  an  irritating  odor 
like  that  of  chlorine  permeated  the  room.  When  the  vapors  condensed 
on  cold  objects,  no  liquid  was  formed,  but  there  appeared  instead  a 
quantity  of  dark  crystals  with  a  luster  surprisingly  like  that  of  a  metal  (45). 

Courtois  noticed  that  the  new  substance  did  not  readily  form  com- 
pounds with  oxygen  or  with  carbon,  that  it  was  not  decomposed  at  red 
heat,  and  that  it  combined  with  hydrogen  and  with  phosphorus.  He 
observed  that  it  combined  directly  with  certain  metals  without  efferves- 
cence and  that  it  formed  an  explosive  compound  with  ammonia.  Al- 
though these  striking  properties  made  him  suspect  the  presence  of  a  new 
element,  he  was  too  lacking  in  self-confidence  to  attempt  a  thorough 
investigation  in  his  poorly  equipped  laboratory  and  too  poor  to  take  the 
time  from  his  business  (11).  He  therefore  asked  two  of  his  Dijon  friends, 
Charles-Bernard  Desormes  and  Nicolas  Clement,  Desormes*  future  son- 

*  The  word  varech  is  at  present  applied  only  to  certain  marine  phanerogams  used 
for  packing  and  upholstering. 


THE  HALOGEN   FAMILY  739 

in-law,  to  continue  his  researches  in  their  laboratory  at  the  Conservatoire 
des  arts  et  des  metiers,  and  allowed  them  to  announce  the  discovery  to 
the  scientific  world  (45,  55). 

In  order  that  chemists  might  have  an  opportunity  to  study  the  new 
substance,  Courtois  generously  presented  some  of  it  to  the  pharmaceutical 
firm  of  Vallee  and  Baget  (13).  He  was  unable  to  prepare  it  fast  enough 
to  supply  the  demand,  however  and  could  sell  only  small  amounts  of  it, 
at  a  price  of  600  francs  per  kilogram.  In  1824  M.  Tissier  the  elder  per- 
fected an  industrial  process  which  in  a  few  months  brought  the  price 
of  iodine  down  to  200  francs  per  kilogram. 

Dr.  Alexandre  Marcet  stated  that  Smithson  Tennant  discovered  the 
presence  of  iodine  in  sea  water  just  before  his  fatal  accident  in  1815 
(128).  In  his  famous  research  on  the  composition  of  sea  water,  J.  G. 
Forchhammer  stated  that  iodine  was  "the  first  element  in  sea  water  dis- 


Jean-Antoine-Claude  Chaptal,  Comte  de 
Chanteloup,  1756-1832.  French  physi- 
cian, chemist,  and  manufacturer  of  salt- 
peter, soda,  and  beet  sugar.  Minister  of 
the  Interior  under  Napoleon.  Author  of 
books  on  chemical  industry. 


covered  not  directly  but  by  the  analysis  of  the  ashes  of  fucoidal  plants, 
which  by  organic  power  had  collected  and  concentrated  it  from  sea 
water"  (98).  In  1825  Christian  Heinrich  Pfaff  of  Kiel  proved  that  the 
water  of  the  Baltic  contains  iodine,  as  Apothecary  Kriiger  of  Rostock 
had  suspected  in  1821  (129,  130). 

Courtois  was  engaged  for  some  years  in  the  manufacture  of  iodine 
compounds  and  other  chemical  reagents,  but  in  1835  he  was  obliged  to 
give  up  his  business  and  go  about  the  city  taking  orders.  According 
to  Fremy,  he  prepared  very  pure  iodine,  gave  specimens  of  it  to  his 


740  DISCOVERY    OF   THE   ELEMENTS 

chemical  friends,  and  noted  its  action  on  organic  substances.  Fremy  also 
said: 

They  have  been  unjust  to  Courtois  in  treating  him  as  a  simple  saltpeter- 
maker;  he  was  a  very  skilful  chemist  (un  chimiste  tres  habile) ;  he  ought  to  have 
been  rewarded  for  his  discovery  of  iodine,  and  not  left  to  die  in  poverty  (12, 
13). 

Courtois  died  in  Paris  on  September  27,  1838.  The  Montyon  prize 
of  six  thousand  francs  which  the  Royal  Academy  had  awarded  him  in  1831 
"for  having  improved  the  art  of  healing"  had  all  been  spent,  and  the 
widow,  poor  and  uneducated,  struggled  against  approaching  deafness  and 
blindness  in  a  vain  attempt  to  earn  her  living  by  lacemaking.  It  is  indeed 
sad  to  know  that  her  last  months  were  spent  in  a  charitable  institution. 

In  the  auditorium  of  the  Dijon  Academy,  harmoniously  decorated 
in  the  style  of  Louis  XIV,  there  occurred  on  November  9,  1913,*  a  solemn 
civic  ceremony  in  honor  of  the  one  hundredth  anniversary  of  the  discovery 
of  iodine.  At  that  time  a  commemorative  plaque  was  placed  on  the 
birthplace  of  Courtois,  and  in  the  following  year  a  street  was  named  for 

him. 

While  Desormes  devoted  most  of  his  time  to  applied  chemistry, 
Clement  (1779-1841)  carried  out  a  classical  research  in  which  he  pre- 
pared the  new  substance  and  made  a  thorough  study  of  its  properties.  In 
his  report  in  1813  he  wrote: 

The  mother  liquor  from  seaweed  ash  contains  quite  a  large  quantity  of  a 
very  peculiar  and  curious  substance;  it  is  easily  extracted;  one  merely  pours 
sulfuric  acid  on  the  mother  liquor  and  heats  the  mixture  in  a  retort  the  mouth 
of  which  is  connected  to  a  delivery-tube  leading  to  a  bulb.  The  substance 
which  is  precipitated  in  the  form  of  a  black,  shining  powder  immediately  after 
the  addition  of  sulfuric  acid,  rises,  when  heated,  in  vapor  of  a  superb  violet 
color.  This  vapor  condenses  in  the  delivery-tube  and  receiver  in  the  form  of 
very  brilliant  crystalline  plates  having  a  luster  equal  to  that  of  crystalline  lead 
sulfide.  Upon  washing  these  plates  with  a  little  distilled  water,  one  obtains  the 
substance  in  the  pure  state  (45,  13). 

Clement  believed  iodine  to  be  an  element  similar  to  chlorine  (12) , 
and  showed  it,  first  to  J.-A.-C.  Chaptal  and  A.-M.  Ampere,  and  later  to 
Sir  Humphry  Davy.  The  proof  of  its  elementary  nature  was  given 
independently  by  Davy  in  England  and  by  Gay-Lussac  in  France.  Davy 
showed  that  iodine  vapor  is  not  decomposed  by  a  carbon  filament  heated 
red-hot  by  a  voltaic  current  (12,  46).  In  his  classical  research,  the 
results  of  which  were  published  in  1814,  Gay-Lussac  prepared  hydrogen 

*  Although  Courtois  discovered  iodine  in  1811,  the  announcement  by  Clement  and 
Desormes  was  not  made  until  two  years  later.  Therefore,  the  centenary  was  observed 
in  1913. 


THE  HALOGEN  FAMILY      741 

iodide  and  showed  that  it  reacts  with  mercury,  zinc,  and  potassium  to 
give  the  corresponding  metallic  iodides,  hydrogen,  and  no  other  product 
(5,39). 

In  1814  Thomas  Charles  Hope  of  Edinburgh  wrote  in  a  letter  to  the 
British  Quaker  chemist  William  Allen:  "I  should  be  very  glad  to  know" 
what  doctrine  you  teach  now  with  regard  to  oxymuriatic  acid.  Are  you 
yet  a  convert  to  chlorine?  I  am  impatient  to  see  Lussac's  paper  on  iodine, 
in  particular  to  learn  how  far  the  facts  respecting  that  substance  go  to 
confirm  the  new  views  of  chlorine.  Lussac  appears  to  be  a  convert  to 
Davy's  sentiments,  and  certainly  the  acquisition  of  one  who  so  strenu- 
ously opposed  them  must  be  accounted  a  very  flattering  occurrence" 
(117). 


Andre-Marie  Ampere,  1775-1836.  French 
physicist,  mathematician,  and  chemist. 
Professor  at  the  Ecole  Polytechnique, 
Paris.  One  of  the  founders  o£  electro- 
dynamics. Inventor  of  the  astatic  needle. 
The  practical  unit  of  current  strength 
was  named  for  him. 


Early  in  the  nineteenth  century  the  use  of  potassium  iodide  as  a 
remedy  for  goiter  was  introduced  by  several  physicians.  William  Prout 
mentioned  in  1834,  in  his  "Chemistry,  Meteorology,  and  the  Function  of 
Digestion  Considered  with  Reference  to  Natural  Theology"  (168),  that 
"Iodine  has  lately  been  much  celebrated  for  its  medicinal  properties," 
and  added  in  a  footnote: 

"It  may  not  be  amiss  also  to  notice,  that  the  author  of  the  present 
volume  first  employed  the  hydriodate  of  potash,  as  a  remedy  for  goitre, 
in  the  year  1816;  after  having  previously  ascertained,  by  experiments 
upon  himself,  that  it  was  not  poisonous  in  small  doses,  as  had  been 


742  DISCOVERY  OF  THE  ELEMENTS 

represented.  Some  time  before  the  period  stated,  this  substance  had  been 
found  in  certain  marine  productions;  and  it  struck  the  author,  that 
burnt  sponge  (a  well-known  remedy  for  goitre)  might  owe  its  properties 
to  the  presence  of  Iodine,  and  this  was  his  motive  for  making  the  trial.  He 
lost  sight  of  the  case  in  which  the  remedy  was  employed,  before  any 
visible  alteration  was  made  in  the  state  of  disease;  but  not  before  some 
of  the  most  striking  effects  of  the  remedy  were  observed.  The  above 
employment  of  the  compounds  of  Iodine  in  medicine  was,  at  the  time, 
made  no  secret;  and  so  early  as  1819,  the  remedy  was  adopted  in  St. 
Thomas'  Hospital,  by  Dr.  Elliotson,  at  the  author  s  suggestion. 


Jean-Frangois  Coindet,  1774-1834.  Swiss 
physician  who  introduced  the  scientific  use 
of  iodine  for  treatment  of  goiter.  Calcined 
sponge  and  other  substances  now  known 
to  contain  iodine  had  long  been  used 
empirically  for  the  same  purpose.  See 
ref.  (110). 


Aesculape,  1913 


The  Dr.  Elliotson  to  whom  Dr.  Prout  was  referring  was  probably 
John  Elliotson  ( 1791-1868 ) . 

In  1820  Dr.  J.-F.  Coindet  of  Geneva  introduced  the  use  of  iodine  in 
the  treatment  of  goiter  (13,  56).  Jean-Frangois  Coindet  was  bora  at 
Geneva,  Switzerland,  in  July,  1774.  After  completing  his  medical  course 
at  Edinburgh  in  1797,  he  returned  to  Geneva,  where  he  practiced  for 
the  rest  of  his  life.  In  1809  he  became  chief  physician  at  the  civil  and 
military  hospital.  Although  his  large  practice  made  heavy  demands  on 
his  time  and  strength,  Dr.  Coindet  never  lost  his  active  interest  in  sci- 
entific research. 

One  day  in  1819*,  when  nineteen-year-old  J.-B.  Dumas  had  charge  of 

*  This  is  the  date  given  by  Van  Tieghem,  ref.    (99);  A.  W.  von  Hofmann,  ref. 
(103),  gave  the  date  as  1818  ( when  Dumas  was  only  eighteen  years  old ) . 


THE   HALOGEN    FAMILY  743 

the  laboratory  at  the  Le  Royer  pharmacy  in  Geneva,  Dr.  Coindet  asked 
him  to  test  some  calcined  sponge  for  iodine.  When  the  boy  obtained 
clear  proof  of  its  presence,  Dr.  Coindet  asked  him  to  suggest  different 
forms  in  which  iodine  could  be  conveniently  administered.  Even  before 
any  iodide  was  commercially  available,  Dumas  proposed  the  tincture  of 
iodine,  potassium  iodide,  and  a  solution  of  iodine  in  potassium  iodide. 
Two  memoirs  on  this  subject  signed  "A.  Le  Royer,  pharmacist,  and  J.-B. 
Dumas,  his  pupil"  were  published  in  1819  and  1820  in  Meisners  Journal 
in  Berne  (99,100). 

In  1820  Dr.  Coindet  published  in  the  Annales  de  Chimie  et  de 
Phijsique  a  paper  entitled  "Discovery  of  a  new  remedy  for  goiter"  (101, 
102).  "A  year  ago,"  said  he,  "while  looking  for  a  formula  in  Cadet  de 
Gassicourt's  work,  I  found  that  Russel  advised  for  goiter  the  use  of  kelp, 
fucus  vesiculosus,  under  the  name  of  vegetable  ethiops.  Not  knowing 
then  what  relation  might  exist  between  this  plant  and  the  sponge,  I 
suspected  by  analogy  that  iodine  must  be  the  active  principle  common 
to  these  two  marine  productions.  ...  Up  to  the  present,  calcined  sponge 
has  formed  the  basis  of  all  the  remedies  for  goiter  which  have  met  with 
any  success.  It  is  Arnaud  de  Villeneuve  who  made  it  known"  (101). 

The  earliest  official  recommendation  of  this  remedy  which  Alexander 
Tschirch  was  able  to  find  was  in  the  eighth  edition  of  the  Augustana 
Pharmacopoeia  of  1623  (104).  The  Chinese  scholar  Li  Shi  Chen,  author 
of  a  famous  pharmacopoeia  (the  Pen  Ts'ao  Kang  Mu,  sixteenth  century 
A.D.),  prescribed  as  a  remedy  for  goiter  a  wine  made  from  sea  plants 
(105).  In  1769  Dr.  Russel  recommended  "vegetable  ethiops"  (charcoal 
made  by  burning  fucoid  seaweeds)  for  the  same  purpose  (13). 

As  early  as  December,  1819,  Dr.  Johann  Castor  Straub,  Professor  of 
Chemistry  at  the  Agricultural  Institute  at  Hofwyl,  Switzerland,  noticed 
that  calcined  sponge  (spongia  usta  off.)  had  an  odor  like  that  of  iodine. 
He  was  soon  able  to  demonstrate  the  presence  in  the  sponge  of  this 
element,  which  had  previously  been  detected  only  in  marine  plants.  He 
therefore  ascribed  the  medicinal  value  of  the  calcined  sponge  to  its  iodine 
content,  and  recommended  the  use  of  artificial  substances  containing 
iodine  as  specific  for  goiter  (104, 106, 107). 

At  about  the  same  time,  Dr.  Andrew  Fyfe  ( 1792-1861 )  of  Edinburgh 
detected  iodine  in  several  species  of  Fucus,  in  a  species  of  conferva,  and 
in  "the  common  sponge  of  the  shops,"  and  published  a  paper  on  it  in  the 
Edinburgh  New  Philosophical  Journal  (108).  After  serving  as  assistant 
to  Professor  Hope,  he  gave  private  lectures  on  chemistry  and  pharmacy 
at  Edinburgh.  From  1844  until  his  death  in  1861  he  occupied  the  chair 
of  chemistry  at  the  University  of  Aberdeen  ( 109 ) . 

Although  calcined  sponge  often  caused  cramps  of  the  stomach, 
Coindet  found  that  sodium  or  potassium  iodide  made  the  goiters  disap- 


744  DISCOVERY  OF  THE  ELEMENTS 

pear  much  more  quickly  and  without  this  deleterious  effect.  "What  is 
the  substance  in  the  sponge  which  acts  as  a  specific  against  goiter?  It 
seemed  probable  to  me/7  he  continued,  "that  it  was  iodine;  I  was  con- 
firmed in  that  opinion  when  I  learned  that,  near  the  end  of  1819,  M.  Fife 
[Fyfe]  of  Edinburgh  found  iodine  in  the  sponge;  as  early  as  six  months 
ago  I  had  confirmed  its  surprising  effects  in  this  malady"  (101 ) . 

Dr.  Coindet  was  one  of  the  founders  of  the  Medical  Society  of  the 
Canton  of  Geneva,  and  was  for  many  years  its  president.  He  was  also 
elected  and  re-elected  to  the  representative  council  of  this  canton.  He 
died  at  Nice  in  1934  (102,  110).  His  son  Dr.  Charles  W.  Coindet,  also 
published  researches  on  the  therapeutic  uses  of  iodine  ( 105,  111 ) . 

In  1814  Jean-Jacques  Colin  and  Henri-Frangois  Gaultier  de  Claubry, 
professor  of  toxicology  at  the  School  of  Pharmacy  in  Paris,  described  the 
blue  substance  produced  when  free  iodine  acts  on  starch,  and  studied 
the  effects  of  temperature  and  of  sulfurous  acid,  hydrogen  sulfide,  and 
other  reagents  on  this  reaction  (131).  In  the  same  year  Friedrich 
Stromeyer  first  applied  this  starch  reaction  to  analytical  chemistry  and 
was  able  to  detect  as  little  as  one  part  of  iodine  in  350,000  to  450,000  parts 

(132). 

In  1825  A.-J.  Balard  detected  iodine  in  "various  marine  mollusks, 
bare  or  testacean,  such  as  the  doris,  the  venus,  oysters,  etc.;  several  corals 
and  marine  plants,  the  gorgonia,  the  zostera  marina,  etc.,  and  especially 
in  the  mother  liquor  of  the  salt  works  supplied  by  the  Mediterranean" 
(133).  This  was  his  first  research,  which  was  soon  followed  by  his 
discovery  of  bromine. 

The  Quarterly  Journal  of  Science  and  the  Arts  for  1823  described  the 
first  discovery  of  iodine  in  a  spring  water:  "The  waters  of  Sales  spring 
in  considerable  quantities  from  an  argilo-calcareous  ground  at  the  foot 
of  a  hillock,  on  the  left-hand  side  of  the  torrent  Staffora,  near  the  road 
to  Godiaso,  not  far  from  Sales,  in  the  province  of  Voghera.  They  are 
turbid  and  of  a  faint  yellow  colour.  They  have  a  strong  odour  approach- 
ing to  that  of  urine,  or  a  muriatic  residuum;  their  taste  is  brackish  and 
sharp;  bubbles  of  air  constantly  rise  from  the  bottom  of  the  reservoir 
containing  them.  ... 

"In  1788  the  Canon  Volta  analyzed  them  and  found  a  twelfth  of 
muriate  of  soda.  In  1820,  M.  Romano  repeated  the  analysis  and  found 
muriate  of  soda,  several  earthy  muriates  [chlorides],  and  a  little  oxide  of 
iron.  M.  Laur.  Angelina  [Laurent  Angelini],  of  Voghera,  on  using  starch 
as  a  reagent,  found  a  blue  colour  produced  in  the  water,  indicating  the 
presence  of  iodine,  and  using  the  process  generally  adopted  with  the 
mother  waters  in  the  manufacture  of  soda,  he  succeeded  in  procuring  a 
certain  quantity  of  iodine  from  the  water.  It  is  remarkable  that  for  a 


THE   HALOGEN    FAMILY  745 

long  time  the  water  of  Sales  has  been  administered  successfully  in 
scrofulous  cases  and  in  cases  of  the  goitre"  (134). 

Angelini's  experiments  were  made  in  1822  and  were  believed  by 
Hermann  Kopp  to  constitute  the  first  discovery  of  iodine  in  a  mineral 
water  (129,  135).  Apothecary  Kriiger  found  it  soon  afterward  in  the 
mother  liquor  of  the  saline  springs  of  Siilzer  in  Mecklenburgh-Schwerin 
(134).  J.  N.  Fuchs  detected  it  in  1823  in  the  rock  salt  of  Hall  in  the  Tyrol 
which  had  been  used  medicinally  since  the  ninth  century  A.D.  ( 105,  129, 
134). 

J.  W.  von  Goethe  never  lost  interest  in  chemistry.  In  the  "Conver- 
sations of  Goethe  with  [Johann  Peter]  Eckermann  and  Soret,"  Soret  states 
that  "Iodine  and  chlorine  occupied  him  particularly;  he  spoke  about  these 
substances  as  if  the  new  discoveries  in  chemistry  had  quite  taken  him 
by  surprise.  He  had  some  iodine  brought  in,  and  volatilized,  before  our 
eyes,  in  the  flame  of  a  taper;  by  which  means  he  did  not  fail  to  make  us 
admire  the  violet  vapour  as  a  pleasing  confirmation  of  a  law  in  his  theory 
of  colours.  .  .  .  The  investigations  which  are  now  being  made  touching 
the  discovery  of  salt  springs  evidently  interested  him"  (136).  At  that 
time  ( 1822 ) ,  Goethe  was  seventy-three  years  old. 

In  July,  1824,  Lanzarote  Island  was  shaken  by  violent  earthquakes 
and  volcanic  eruptions.  When  R.  Brandes  analyzed  some  of  the  volcanic 
sal  ammoniac  which  formed  a  thin  yellow,  orange,  or  brown  crust  over 
the  lava,  he  found  it  to  contain  both  selenium  and  iodine  (137).  When 
he  opened  the  small  chest  in  which  E.  Walte  of  Bremen  had  shipped 
specimens  of  these  volcanic  minerals  to  him,  Brandes  noticed  a  faint  odor 
of  iodine,  which  was  easily  identified  after  gentle  warming  of  the  sal 
ammoniac  (137, 138). 

An  Iodide  Mineral  As  late  as  1822  Christian  Heinrich  Pfaff  of  Kiel, 
in  his  "Handbuch  der  analytischen  Chemie,"'  classified  the  iodides  with 
the  "salts  which  up  to  the  present  have  not  been  found  in  the  mineral 
realm,  but  may  occur  there"  (139).  Berzelius  too  suggested,  in  his  "New 
Mineral  System"  in  1825,  that  iodine  might  some  day  be  discovered  to 
be  a  mineral  production.  A.  M.  del  Rio,  in  his  Spanish  translation  of  this 
work  two  years  later,  made  the  following  comment:  "This  has  already 
been  verified  in  this  America.  M.  Vauquelin  has  found  181/2  per  cent 
of  iodine  in  a  Mexican  fossil  which  is  embedded  in  the  serpentine  and 
was  labeled  native  silver.  With  such  a  meager  description  and  in  such 
a  vast  republic,  it  was  not  easy  to  locate  the  vein.  Fortunately  I  remem- 
bered the  native  and  horn  silver  in  serpentine  which  C(itizen)  J.  M. 
Herrera,  my  pupil  and  friend  so  esteemed  for  his  learning  and  integrity, 
brought  me  from  Albarradon,  near  Mazapil  in  the  state  of  Zacatecas; 
and  knowing  that  artificial  silver  iodide  looks  like  horn  silver,  or  silver 
chloride,  I  subjected  it  to  the  blowpipe,  and  as  soon  as  the  heat  was 


746  DISCOVERY  OF  THE  ELEMENTS 

applied,  it  melted  and  became  reddish,  giving  off  vapor  which  tinged  the 
flame  with  a  handsome  violet,  and  spread  little  globules  of  silver  into  the 
charcoal.  Even  the  specimen  which  by  its  color  and  luster  appeared  to 
be  native  and  was  rather  translucent  gave  traces  of  iodine;  the  label 
native  silver  was  not  then  so  absurd.  Therefore  at  least  that  from 
Albarradon  is  silver  iodide,  which  does  not  dissolve  in  ammonia  either. 
My  dear  friend  Citizen  Bustamante  has  just  observed  the  violet  flame 
with  a  brownish  white  lead  from  the  mine  at  Catorce"  (140). 

The  "native  silver  in  serpentine"  in  which  Vauquelin  discovered  iodine 
had  been  obtained  from  Joseph  Tabary,  a  dealer  in  Mexican  and  South 
American  minerals  (137),  In  an  attempt  to  ascertain  the  exact  locality 
from  which  this  mineral  had  been  obtained,  D.-F.  Arago  questioned  some 
young  Mexican  army  officers  who  had  been  sent  by  their  government  to 
study  in  Paris.  To  his  surprise,  one  of  them,  Captain  Yniestra,  was  able 
to  give  the  following  clear  and  definite  reply: 

"At  the  time  when  Vauquelin  discovered  iodine  in  a  silver  mineral 
from  Mexico,  M.  del  Rio,  professor  of  mineralogy  in  our  school  of  mines, 
confirmed  the  presence  of  the  same  substance  in  the  horn  silver  of 
Albarradon.  This  latter  name  is  that  of  a  district  near  that  of  Mazapil,  in 
the  department  of  Zacatecas.  The  name  of  the  mountain  of  Albarradon 
where  the  silver  mine  is  located  is  Temeroso. 

"Our  famous  Bustamante  also  found  iodine  in  a  white  lead  from  the 
mine  at  Catorce,  situated  in  the  department  of  Guanajuato.  In  1834,  I 
myself,  together  with  M.  Herrera,  made  the  quantitative  analysis  of  the 
latter  mineral.  .  .  . 

"I  do  not  know  whether  you  have  heard  that  iodine  has  been  dis- 
covered in  Mexico  in  the  sabila  and  in  the  romeritos.  The  sabila  is  a 
plant  similar  to  the  magueys  ( agaves )  which  grow  on  the  plains  and  at 
the  top  of  the  mountains.  The  romeritos  are  a  kind  of  barilla  which  grow 
in  the  floating  gardens  on  the  fresh-water  lakes  near  the  capital.  Every- 
one eats  them  during  Lent."  The  preceding  letter  was  published  in  the 
Annales  de  Chimie  et  de  Physique  in  1836  (141). 

Diffusion  of  Iodine  in  Nature.  The  presence  of  iodine  in  the  Chile 
saltpeter  deposits  was  first  noted  by  A.  A.  Hayes,  who  found  it  to  be 
present  as  iodate  (142, 143). 

The  occurrence  of  iodine  in  igneous  rocks  was  first  conclusively 
demonstrated  by  Armand  Gautier  in  1901  (144).  Since  it  had  previously 
been  detected  in  volcanic  emanations  and  lavas  and  in  the  sludges  from 
mud  volcanos,  and  since  it  is  often  associated  with  boric  acid,  Gautier 
concluded  that  it  must  come  from  great  depths  and  that  therefore  it  ought 
to  be  possible  to  detect  it  in  the  most  ancient  rocks.  His  results  showed 
that  "iodine,  which  exists  in  all  the  granites  we  have  examined,  seems 
not  to  form  a  constituent  part  of  either  their  micas  or  of  the  apatites  which 


THE  HALOGEN   FAMILY  747 

are  often  abundantly  mingled  in  these  rocks.  This  element  is  evidently 
very  variable,  as  any  substance  must  be  which  is  entrained  in  the  form 
of  a  mere  impurity"  (144). 

The  detailed  researches  of  A.  Chatin  and  subsequent  studies  of 
T.  von  Fellenberg  showed  that  iodine  in  small  amounts  occurs  everywhere 
—in  rocks,  in  the  sea,  and  in  all  organisms  (145).  According  to  V.  M. 
Goldschmidfs  theory  of  the  geochemical  distribution  of  the  elements, 
concentric  shells  or  phases  were  formed  as  the  earth  solidified.  The 
siderophile  elements  were  concentrated  in  the  iron  kernel,  the  chalcophile 
elements  in  the  sulfide  shell,  the  lithophile  elements  in  the  silicate  mass, 
and  the  atmophile  elements  in  the  steam  phase.  Gulbrand  Lunde  stated 
that  "iodine  is  an  element,  as  far  as  we  hitherto  know  the  only  one,  which 
on  the  earth's  division  into  phases  did  not  show  remarkable  affinity  to 
any  of  the  phases.  It  became  part  of  them  all,  but  showed,  however, 
more  conspicuous  atmophile  and  lithophile  than  chalcophile  and  sidero- 
phile characteristics"  (144).  Iodine  is  also  present  in  the  biosphere,  usu- 
ally in  greater  concentration  than  in  the  rocks  (144).  It  is  probably  not 
essential  in  plant  nutrition  (146). 

BROMINE 

Centuries  before  the  element  bromine  was  discovered,  one  of  its 
organic  compounds,  Tyrian  purple,  was  used  as  a  rich  costly  dye  pre- 
pared from  a  white  juice  secreted  by  the  Mediterranean  mollusk,  the 
straight-spined  Murex  (M.  brandaris  Linne)  (91, 166).  Strabo  described 
the  Tyrian  dyeworks  in  his  Geography,  and  the  product  was  mentioned 
frequently  in  the  Bible  (Ezek.  27,  7,  16)  (92).  In  1909  H.  Friedlander 
of  Vienna  discovered  that  this  royal  dye  from  Murex  brandaris  is  identical 
with  the  6:6'  dibrom  indigo  which  F.  Sachs  of  Berlin  and  his  collaborators 
had  prepared  only  five  yea*rs  previously  from  p-bromo-o-nitrobenzalde- 
hyde(93,94,95). 

In  1825  Carl  Lowig,  a  new  student  who  had  just  entered  the  chemical 
laboratory  at  Heidelberg,  won  the  immediate  interest  of  Leopold  Gmelin, 
his  professor.  Lowig  had  brought  with  him  from  his  home  at  Kreuznach 
a  red  liquid  which  he  had  prepared  by  passing  chlorine  into  the  mother 
liquor  from  a  salt  spring  and  shaking  it  out  with  ether.  The  red  liquid 
had  remained  after  he  had  distilled  off  the  ether.  Professor  Gmelin  asked 
him  to  prepare  more  of  it  in  order  to  study  its  properties,  but  in  the 
meantime  there  appeared  in  1826  in  the  Annales  de  chimie  et  de  physique 
a  paper  by  A.-J.  Balard  announcing  the  discovery  of  bromine  (28,  36,  57). 
The  properties  which  Balard  ascribed  to  bromine  were  identical  with  those 
Lowig  had  observed  for  the  substance  from  Kreuznach.  This  explains 
why  Balard,  instead  of  Lowig,  is  regarded  as  the  discoverer  of  bromine. 


748 


DISCOVERY  OF  THE  ELEMENTS 


Carl  Lowig  was  born  at  Kreuznach  on  March  17,  1803.  In  his  youth 
he  studied  pharmacy,  but  his  later  study  was  confined  entirely  to  chem- 
istry. He  continued  his  investigation  of  the  compounds  of  bromine  for 
several  years,  and  in  1829  published  a  monograph  on  "Bromine  and  Its 
Chemical  Relations." 

In  1833  he  was  called  to  the  newly  founded  University  of  Zurich, 
where,  in  spite  of  the  very  meager  equipment,  he  analyzed  many  Swiss 
mineral  waters  and  published  monographs  on  them.  His  "Chemie  der 
organischen  Verbindungen,"  based  on  the  radical  theory,  "was  the  Beil- 
stein  of  that  time,  and  was  to  be  found  in  the  hands  of  every  chemist" 
(57,66). 


Carl  Lowig,*  1803-1890.  Professor  of 
chemistry  at  Heidelberg,  Zurich,  and 
Breslau.  He  prepared  bromine  in  1825, 
but  before  his  investigation  was  com- 
pleted Balard  had  announced  the  dis- 
covery. Lowig  discovered  bromine  hy- 
drate, bromal  hydrate,  and  bromoform, 
and  was  the  founder  of  the  Silesian  chem- 
ical industry  and  of  the  Goldschmieden 
alumina  works  at  Deutsch-Lissa. 


In  1853  Lowig  became  Robert  Buns  en's  successor  at  Breslau.  He 
was  given  offices  of  great  responsibility,  and  served  as  Rector  both  at 
Zurich  and  at  Breslau.  He  taught  six  semesters  at  Heidelberg,  forty  at 
Zurich,  and  seventy-two  at  Breslau,  and  hoped  to  teach  two  more  in  order 
to  make  the  total  one  hundred  and  twenty.  This  hope  was  not  to  be 
realized,  however,  for,  while  walking  in  the  zoological  garden,  he  failed 

*  The  author  is  indebted  to  Dr.  Max  Speter  of  Berlin   and  Dr.  Julius   Meyer  of 

Breslau  for  their  assistance  in  obtaining  this  portrait,  the  original  of  which  hangs 

in  the  Chemical  Institute   at  Breslau.     Some  valuable  information   about   Lowig's 

scientific  activities  was  also  graciously  contributed  by  Professor  Meyer. 


THE  HALOGEN   FAMILY  749 


t 

(f— 


Antoine-Jerome  Balard,  1802-1876.  French  chemist  and  pharmacist  who 
discovered  bromine.  Professor  of  chemistry  at  the  Sorbonne  and  at  the 
College  de  France.  He  discovered  hypochlorous  acid,  worked  out  the  con- 
situation  of  Javelle  water,  and  perfected  industrial  methods  for  extracting 
various  salts  from  sea  water. 


750 


DISCOVERY  OF  THE  ELEMENTS 


One  of  the  Laboratories   of  Mineralogical   Chemistry   at   the   Sorbonne. 

Balard,  the  discoverer  of  bromine,  Moissan,  the  discoverer  of  fluorine,  Lamy 

who  isolated  thallium,  and  M.  and  Mme.  Curie,  the  discoverers  of  radium, 

ah1  taught  at  the  Sorbonne.. 

to  notice  some  steps,  fell,  and  received  a  fracture  of  the  hip  from  which  he 
never  recovered.  He  died  on  March  27,  1890,  ten  days  after  his  eighty- 
seventh  birthday  (57). 

Antoine- Jerome  Balard  (14),  was  born  at  Montpellier  on  September 
30,  1802.  Since  his  parents  were  poor,  he  was  adopted  and  educated  by 
his  godmother.  He  studied  at  the  College  of  Montpellier  for  a  time,  and 
at  the  age  of  seventeen  years  he  became  a  preparateur  at  the  Ecole  de 
Pharmacie,  where  he  graduated  in  1826  (47,  66,  68). 

In  1824,  while  studying  the  flora  of  a  salt  marsh,  he  noticed  a  deposit 
of  sodium  sulfate  which  had  crystallized  out  in  a  pan  containing  mother 
liquor  from  common  salt.  In  an  attempt  to  find  a  use  for  these  waste 
liquors  he  performed  a  number  of  experiments,  and  noticed  that  when 
certain  reagents  were  added,  the  mother  liquor  became  brown.  His 
investigation  of  this  phenomenon,  made  when  he  was  only  twenty-three 
years  old  led  to  the  remarkable  discovery  which  P.-L.  Dulong  described 
in  the  following  letter  to  Berzelius  written  on  July  1,  1826: 

.  .  .  But  here  is  another  piece  of  recent  news.  ...  It  is  a  new  simple 
body  which  will  find  its  place  between  chlorine  and  iodine.  The  author  of  this 
discovery  is  M.  Ballard  of  Montpellier.  This  new  body,  which  he  calls  muride, 
is  found  in  sea  water.  He  has  extracted  it  from  the  mother  liquor  of  Mont- 
pellier brines  by  saturating  them  with  chlorine  and  distilling.  He  obtains  a 
dark  red  liquid  substance  boiling  at  47°.  The  vapor  resembles  that  of  nitrous 
acid.  Its  specific  gravity  is  3.  One  preserves  it  under  concentrated  sulfuric 


THE   HALOGEN   FAMILY  751 

acid.    It  combines  with  metals  and  gives  compounds  sensibly  neutral,  of  which 
several  are  volatile,  notably  the  muride  of  potassium  .   .   .   (15). 

Since  the  name  muride  did  not  find  favor  with  the  French  Academy's 
committee,  consisting  of  Vauquelin,  Thenard,  and  Gay-Lussac,  the  ele- 
ment is  now  known  as  bromine,  meaning  bad  odor  (12,  26). 

When  Balard  made  this  eventful  discovery,  he  was  merely  an  obscure 
young  assistant  in  the  chemistry  department  of  his  college.  He  had 
noticed  that  when  the  lye  from  the  ash  of  Fucus  was  treated  with  chlorine 
water  and  starch,  two  layers  appeared  in  the  solution.  The  lower  layer 
was  blue  because  of  the  action  of  the  starch  on  the  iodine,  and  the  upper 
one  was  intensely  orange.  When  he  treated  the  mother  liquor  from  the 
salt  works  in  the  same  manner,  he  again  observed  this  orange  zone  above 
the  blue  one.  To  separate  the  new  substance,  he  passed  a  current  of 
chlorine  gas  into  the  mother  liquor  from  the  saltworks,  and  shook  the 
mixture  until  the  new  orange-colored  substance  passed  into  the  ether 
layer.  After  removal  of  the  aqueous  layer,  he  added  caustic  potash  to 
the  orange-colored  ethereal  layer.  By  evaporation,  he  obtained  cubic 
crystals  of  the  soluble  salt  now  known  as  potassium  bromide. 

The  young  assistant  concluded  that  there  were  only  two  possible 
explanations:  The  yellow  substance  must  either  be  a  compound  of 
chlorine  with  some  constituent  of  the  lye,  or  it  must  be  a  new  element 
just  liberated  from  one  of  its  compounds  by  the  chlorine,  which  had 
replaced  it.  Balard  at  first  favored  the  first  hypothesis  and  thought  that 
he  had  an  iodide  of  chlorine,  but,  when  all  attempts  to  decompose  the 
new  substance  failed,  he  concluded  that  his  second  explanation  must  be 
the  correct  one  and  that  the  new  element  must  be  similar  to  iodine  and 
chlorine  (28). 

Balard  found  that  bromine  can  be  shaken  out  of  solution,  first  with 
ether  and  then  with  caustic  potash.  Upon  heating  the  resulting  potassium 
bromide  with  sulfuric  acid  and  manganese  dioxide,  one  can  distil  the 
bromine  off  and  condense  it  as  a  red  liquid  or  collect  it  in  water  (12). 
Just  as  mercury  is  the  only  common  metal  whose  liquid  phase  is  stable 
at  room  temperature,  bromine  is  the  only  liquid  non-metal. 

In  his  first  research  on  bromine,  published  in  the  Annales  de  Chimie 
et  de  Physique  in  1826,  Balard  prepared  and  characterized  many  of  its 
compounds  and  described  some  of  its  most  important  natural  sources. 
This  astonishingly  rapid  progress  was  possible  only  because  of  the  close 
resemblance  of  bromine  to  chlorine  and  iodine,  which  were  already  well 
known. 

"Bromine,"  said  he,  "is  found  in  very  minute  amounts  in  sea  water. 
The  mother  liquor  of  the  salt  works  itself,  although  it  has  been  singularly 
diminished  in  volume  by  the  evaporation  which  has  permitted  the  salt  to 


752  DISCOVERY  OF  THE  ELEMENTS 

deposit,  and  although  the  latter  has  not  carried  down  appreciable  amounts 
of  it,  contains  only  a  little  of  it.  The  nature  of  the  methods  by  which  one 
can  extract  it  seems  to  indicate  that  it  is  present  in  the  form  of  hydro- 
bromic  acid,  and  some  considerations  lead  me  to  believe  that  this  acid  is 
combined  with  magnesia. 

"As  a  matter  of  fact/'  continued  Balard,  "when  one  strongly  calcines 
the  residue  from  the  evaporation  of  the  water  from  the  salt  works  it 
loses  its  ability  to  liberate  bromine  in  contact  with  chlorine.  If  one 
recalls  that  the  hydro-bromates  [bromides]  I  have  examined,  with  the 
exception  of  that  of  magnesia,  are  not  at  all  decomposed  by  heat,  one 
will  be  tempted  to  suppose  that  the  water  of  the  salt  works  actually 
contained  this  compound. 

"The  plants  and  animals  living  in  the  ocean  also  contain  bromine. 
The  ashes  of  plants  growing  in  the  Mediterranean  all  give  a  yellow  tinge 
when  one  treats  the  product  of  their  lixiviation  with  chlorine.  I  have  also 
seen  the  same  color  produced  on  treating  with  this  reagent  the  solution 
of  the  ash  of  lanthina  violacea,  a  testacean  mollusk  which  I  owe  to  the 
kindness  of  M.  Auguste  Berard,  and  which  that  distinguished  officer 
collected  at  the  Island  of  St.  Helena  on  his  second  voyage  around  the 
world. 

"I  have  been  able  to  extract  considerable  quantities  of  bromine  from 
the  mother  liquors  of  the  soda  kelp  which  serves  for  the  extraction  of 
the  iodine.  Finally,  it  has  seemed  to  me  that  the  product  of  the  evapora- 
tion of  a  mineral  water  from  the  eastern  Pyrenees,  which  was  strongly 
saline,  became  yellow  in  contact  with  chlorine.  If  the  bromine  actually 
existed  in  a  water  of  this  kind,  one  might  hope  to  encounter  it  in  the 
salt  springs  properly  so  called,  and  especially  in  the  mother  liquor  of  the 
rock  salt.  I  have  lacked  material  to  verify  it.  All  this  makes  it  very 
likely  that  bromine  will  be  found  in  a  large  number  of  marine  productions 
or  those  of  submarine  origin"  (28). 

The  French  Academy's  report  of  the  meeting  of  Monday,  August 
14, 1826,  signed  by  Vauquelin,  Thenard,  and  Gay-Lussac,  reads  as  follows: 

If  the  few  experiments  which  we  have  been  able  to  perform  have  not 
afforded  us  that  certainty  of  the  existence  of  bromine  as  a  very  simple  body 
which  in  the  present  day  is  properly  required,  we  consider  it  at  least  very 
probable  that  it  is  so.  The  memoir  of  M.  Balard  is  extremely  well  drawn  up, 
and  the  numerous  results  which  he  relates  would  not  fail  to  excite  great  interest, 
even  if  it  should  be  proved  that  bromine  is  not  a  simple  body.  The  discovery 
of  bromine  is  a  very  important  acquisition  to  chemistry,  and  gives  M.  Balard 
honorable  rank  in  the  career  of  the  sciences.  We  are  of  the  opinion  that  this, 
young  chemist  is  every  way  worthy  of  the  encouragement  of  the  Academy,  and 
we  have  the  honor  to  propose  that  his  memoir  shall  be  printed  in  the  Recueil 
des  Savants  Strangers  (16 ?  29) . 


THE   HALOGEN   FAMILY  753 

In  the  same  report  Gay-Lussac,  Thenard,  and  Vauquelin  stated  "We 
have  also  obtained  bromine,  by  the  process  described  by  M.  Balard,  by 
treating  the  mother  liquors  of  the  salt  gardens  (marais  solans]  of  the 
plain  of  Aren  which  had  been  sent  to  us  by  our  colleague  M.  d'Arcet"  (29). 

In  1842  Balard  succeeded  Thenard  at  the  Sorbonne,  and  in  1851  he 
accepted  a  professorship  at  the  College  de  France  (36).  He  discovered 
hypochlorous  acid,  worked  out  the  constitution  of  Javelle  water  (44), 
and  perfected  industrial  methods  for  the  extraction  of  various  salts  from 
sea  water.  He  worked  for  twenty  years  at  these  technical  researches, 
and  extracted  sodium  sulfate,  the  basis  of  the  soda  industry,  directly  from 
sea  water.  He  also  extracted  potassium  salts  from  the  sea  water,  and  his 
artificial  potash,  entering  into  competition  with  that  from  the  ashes  of 
plants,  soon  lowered  the  price.  Before  the  discovery  of  the  Stassfurt 
deposits  in  1858,  all  the  bromine  used  by  photographers  was  prepared 
by  Balard's  method. 

The  memory  of  his  early  poverty  made  Balard  economical  in  his 
researches  and  -ascetic  in  his  manner  of  living.  Although  he  survived 
his  three  children  and  his  wife,  his  stepchildren  were  a  great  consolation 
to  him  in  his  old  age.  He  died  in  1876,  honored  because  of  his  achieve- 
ments and  loved  because  of  his  generosity,  modesty,  and  warmth  of 
heart  (47).  In  his  eulogy,  J.-B.  Dumas  mentioned  Balard's  love  for  the 
sea:  "His  thinking  always  drew  him  to  the  sea;  he  would  have  liked 
to  live  near  it,  he  said,  in  order  to  fathom  its  chemical  history;  and,  as 
soon  as  a  free  moment  permitted,  he  took  the  train  to  become  elated  by 
the  effluvia  of  the  Mediterranean"  (96). 

The  glory  due  to  Balard  for  his  discovery  of  bromine  is  enhanced 
when  one  knows  that  the  great  Justus  von  Liebig  just  missed  it  Several 
years  before,  a  German  firm  had  asked  Liebig  to  examine  the  contents 
of  a  certain  bottle,  and  he  had  concluded,  without  thorough  study,  that 
the  substance  was  iodine  chloride.  When  he  heard  of  the  discovery  of 
bromine,  he  immediately  recognized  his  error  and  placed  the  bottle  in  a 
special  case  which  he  called  his  "cupboard  of  mistakes"  (11).  Hence, 
when  his  dear  friend  Friedrich  Wohler  a  few  years  later  just  missed  dis- 
covering vanadium,*  Liebig  knew  how  to  sympathize  with  him. 

As  soon  as  he  had  read  Balard's  paper  on  bromine,  Liebig  examined 
the  brine  from  Theodorshalle  near  Kreuznach  and  prepared  nearly  twenty 
grams  of  bromine.  His  experiments  led  him  to  conclude,  as  Balard  had 
done,  that  it  must  be  a  simple  substance  (27).  "I  know  a  chemist,"  said 
he,  years  later  (referring  to  himself),  "who  during  a  visit  to  Kreuznach 
occupied  himself  with  the  investigation  of  the  saline  mother  liquors  there; 
he  found  iodine  in  them  and  observed  that  the  iodine-starch,  when  left 

*  See  also  Chapter  13.  pp.  353-5. 


754  DISCOVERY  OF  THE  ELEMENTS 

over  night,  acquired  a  fire-yellow  color.  ...  A  few  months  later,  he 
received  Herr  Balard's  beautiful  research  and  was  in  a  position  that  very 
day  to  make  known  a  series  of  experiments  on  the  relation  of  bromine  to 
iron,  platinum,  and  carbon;  for  Balard's  bromine  stood  in  his  laboratory 
labeled  liquid  iodine  chloride.  Since  then  he  makes  no  more  theories 
unless  they  can  be  directed  and  supported  by  unambiguous  experiments" 
(97).  Liebig's  first  paper  on  bromine  was  published  in  the  Annales  de 
chimie  et  de  physique  in  1826  (27). 

Another  chemist  who  just  missed  discovering  bromine  was  J.  R.  Joss, 
who  in  1824,  and  again  in  January,  1826,  had  recorded  in  his  laboratory 
notes  the  appearance  of  a  red  color  in  some  hydrochloric  acid  prepared 
from  gray  Hungarian  rock  salt  and  Bohemian  fuming  sulfuric  acid.  At 
the  time,  he  attributed  this  color  to  the  possible  presence  of  selenium 
from  the  sulfuric  acid.  After  Balard's  discovery,  however,  he  made  further 
experiments  with  the  same  materials  and  became  convinced  that  the 
red  color  must  be  due  to  bromine.  His  attempts  to  obtain  more  of  the 
bromine-containing  rock  salt  were  unsuccessful  (147). 

After  the  publication  of  Balard's  original  paper,  W.  Meissner  of 
Halle  recalled  that  he,  too,  had  observed  an  orange  color  when  he  had 
added  sulfuric  acid  and  starch  to  the  water  of  the  salt  spring  at  Halle 
(154).  Professor  Geiger  of  Heidelberg  soon  detected  bromine  in  the 
spring  at  Rappenau.  When  Dr.  C.  Fromherz  of  Freiburg  investigated 
some  brines  sent  to  him  by  Althaus  of  Durrheim,  inspector  of  the  salt- 
works, he  isolated  bromine  from  the  mother  liquors  from  Durrheim  and 
Schweningen  and  believed  that  it  was  originally  present  in  the  form  of 
magnesium  bromide.  He  also  detected  bromine  in  the  salt  springs  of 
Rappenau,  Wimpfen,  Offenau,  and  Jaxfeld  (148). 

Bromine  from  Sea  Water.  Balard  recognized  in  1826  that  bromine 
is  present  in  low  concentration  in  sea  water.  Professor  Gmelin  of 
Tubingen  detected  it  in  water  from  the  Dead  Sea,  a  discovery  which 
was  promptly  confirmed  by  S.  F.  Hermbstadt  of  Berlin  (149).  In  1934 
the  Dow  Chemical  Company  successfully  extracted  bromine  commer- 
cially from  raw  ocean  water  at  Kure  Beach,  North  Carolina  (150). 

A  Bromide  Mineral.  In  1841  Pierre  Berthier  of  Nemours  ( 1772-1862 ) 
discovered  the  first  mineral  known  to  contain  bromine.  "The  district  of 
Plateros,"  said  he,  "which  is  situated  17  leagues  from  Zacatecas  and  !1/2 
leagues  north  of  Fresnillo,  differs  from  the  other  mining  districts  in  the 
nature  of  the  ore  it  contains.  The  silver  in  this  ore  is  found  in  two  differ- 
ent states:  first,  native  and  disseminated  in  very  small  particles  in  a 
gray,  compact,  highly  plumbiferous  mass;  the  Mexicans  then  call  it 
plata  azul  (blue  silver);  secondly  and  principally,  in  the  form  of  a  com- 
pound occurring  in  little  olive-green  or  yellowish  crystals  called  plata 


THE  HALOGEN   FAMILY  755 

verde  (green  silver),  which  was  believed  to  be  silver  chloride  but  which 
I  have  recognized  as  perfectly  pure  bromide  .  .  ."  ( 151 ) . 

When  Berthier  treated  a  specimen  of  this  ore  from  the  San  Onofe 
Mine  with  an  excess  of  hot  ammonium  hydroxide,  he  observed,  mixed  with 
the  metallic  silver,  a  green  powder  which  had  been  only  incompletely 
attacked.  "This  was  the  circumstance,"  said  he,  "which  drew  my  attention 
to  the  ore  from  Plateros  and  which  led  me  to  realize  that  the  substance 
which  had  been  taken  for  silver  chloride  is  pure  bromide,  without  admix- 
ture of  chloride  or  iodide,  a  substance  which  had  not  yet  been  met  with- 
in the  mineral  realm  and  which  therefore  constitutes  a  new  species"  (151 ) . 
Berthier  learned  that  this  mineral  is  not  rare  in  Mexico  but  is  often 
found  in  beautiful  cubic  and  octahedral  crystals.  He  also  found  the 
same  mineral  at  Huelgoeth,  Department  of  Finistere,  France,  and  dis- 
covered some  of  it  among  the  Chilean  silver  minerals  which  Ignaz 
Domeyko,  professor  of  chemistry  at  the  College  of  Coquimbo,  had  sent 
to  the  School  of  Mines  at  Paris  (151,  152).  The  mineral  which  Berthier 
analyzed  was  evidently  bromyrite  ( silver  bromide ) . 

Bromine  in  Animals.  In  1920  A.  Damiens  detected  bromine  in  the 
blood,  lungs,  kidneys,  and  other  organs  of  normal  dogs,  oxen,  partridges, 
chickens,  and  human  beings.  He  did  not  observe  any  tendency  of  this 
halogen  to  accumulate  as  iodine  does  in  the  thyroid  gland  ( 153 ) . 

FLUORINE 

In  his  "Bermannus",  Georgius  Agricola  in  1529  described  the  use  of 
fluorspar  as  a  flux:  "Bermannus.— These  stones  are  similar  to  gems,  but 
less  hard.  .  .  .  Our  miners  call  them  fluores,  not  inappropriately  to  my 
mind,  for  by  the  heat  of  fire,  like  ice  in  the  sun,  they  liquefy  and  flow 
away.  They  are  of  varied  and  bright  colors.  .  .  .  Anton.— What  is  the  use 
of  fluores?  Bermannus.— They  are  wont  to  be  made  use  of  when  metals 
are  smelted,  as  they  cause  the  material  in  the  fire  to  be  much  more 
fluid... "  (70). 

In  1676  Johann  Sigismund  Elsholtz  (or  Elsholz)  informed  the  mem- 
bers of  the  Imperial  Society  for  Investigating  Nature  ( Societati  Imperiali 
Naturae  Curiosorum)  "that  he  was  acquainted  with  a  phosphorus  which 
had  its  light  neither  from  the  sun  nor  from  fire,  but  which,  when  heated 
on  a  metal  plate  over  glowing  coals,  shone  with  a  bluish-white  lustre;  so 
that  by  strewing  the  powder  of  it  over  paper,  one  might  form  luminous 
writing'  (71,72,113). 

In  his  history  of  the  discovery  of  phosphorus,  G.  W.  Leibniz  stated 
in  1710:  "I  also  showed  this  inquisitive  prince  [Duke  Johann  Friedrich] 
another  kind  [of  phosphorus]  which  one  might  call  thermophosphorus. 


756  DISCOVERY  OF  THE  ELEMENTS 

One  draws  letters  and  figures,  for  example,  on  an  iron  plate  with  a  certain 
flux  in  the  mines;  lays  the  plate  on  glowing  coals;  whereupon  they  shine, 
even  though  the  plate  is  not  heated  to  redness"  (73).  An  editorial  foot- 
note to  this  article  in  Crell's  Neues  chemisches  Archiv  in  1784  stated  that 
this  flux  was  undoubtedly  fluorspar. 

As  early  as  1670  Heinrich  Schwanhard  of  Nuremberg,  a  member  of 
a  famous  family  of  glass  cutters,  found  that  when  he  treated  this  mineral 
with  strong  acids,  the  lenses  of  his  spectacles  became  etched  (71,  74). 
This  led  him  to  discover  and  perfect  a  new  means  of  etching  glass  without 
a  diamond  or  any  abrasive.  In  his  "History  of  Inventions,"  Johann  Beck- 
mann  described  the  process  as  follows:  "At  present,"  said  he,  "the  glass 
is  covered  with  a  varnish,  and  those  figures  which  one  intends  to  etch  are 
traced  out  through  it;  but  Schwanhard,  when  the  figures  were  formed, 
covered  them  with  varnish,  and  then  by  his  liquid  corroded  the  glass 
around  them;  so  that  the  figures,  which  remained  smooth  and  clear, 
appeared  when  the  varnish  was  removed,  raised  from  a  dim  or  dark 
ground"  (71 ).  Schwanhard  raised  this  art  to  a  high  degree  of  perfection, 
and  depicted  people,  animals,  flowers,  and  herbs  in  relief  on  the  glass 
(75).  He  did  this  work  only  for  Emperor  Charles  II. 

The  formula  for  Matthaus  Pauli's  glass-etching  fluid  was  made  public 
in  1725  (76).  Beckmann  then  quoted  the  following  recipe  from  page  107 
of  the  Ereslauer  Sammlung  zur  Natur-  und  Medicin-Geschichte  for  Janu- 
ary, 1725:  "When  spiritus  nitri  per  distillationem  has  passed  into  the  re- 
cipient, ply  it  with  a  strong  fire,  and  when  well  dephlegmated,  pour  it,  as 
it  corrodes  ordinary  glass,  into  a  Waldenburg  flask;  then  throw  into  it  a 
pulverized  green  Bohemian  emerald,  otherwise  called  hesphorus  (which, 
when  reduced  to  powder  and  heated,  emits  in  the  dark  a  green  light),  and 
place  it  in  warm  sand  for  twenty-four  hours  .  .  ."  (71,  74).  The  "Bohe- 
mian emerald"  was  undoubtedly  green  fluorspar.  Fredrick  Accum  pub- 
lished an  article  in  Nicholsons  Journal  for  1800  on  the  antiquity  of  the 
art  of  etching  by  means  of  hydrofluoric  acid  (74). 

In  1768  A.  S.  Marggraf  made  the  first  chemical  investigation  of 
fluorite,  distinguished  it  from  heavy  spar  and  selenitic  spar  (sulfates  of 
barium  and  calcium),  and  showed  that  it  is  not  a  sulfate  ( 77,  78) .  When 
he  distilled  pulverized  fluorspar  with  sulfuric  acid  from  a  glass  retort, 
the  glass  was  badly  attacked  and  even  perforated.  He  noticed  that  an 
"earth"  [silica]  appeared  in  the  receiver,  and  therefore  concluded  that 
the  sulfuric  acid  had  liberated  a  volatile  earth  from  the  fluorspar  (77). 

In  1771  C.  W.  Scheele  investigated  a  green  variety  of  fluorspar  from 
Garpenberg  and  a  white  one  from  Gislof  in  Scania.  He  found  that  the 
green  specimen  contained  a  trace  of  iron  but  that  the  white  one  did  not. 
When  he  heated  the  pulverized  mineral  with  oil  of  vitriol  [sulfuric  acid], 
he  noticed  that  the  inner  surface  of  the  glass  retort  became  corroded, 


THE  HALOGEN   FAMILY 


757 


Courtesy  Wilhelm  Prandtl 

Johann  Sigismund  Elsholtz,  1623-1688.  Scientific  author- 
ity at  the  court  of  the  Elector  of  Brandenburg.  A  pam- 
phlet which  he  had  printed  at  Berlin  in  1676  is  the 
earliest  publication  concerning  elementary  phosphorus 
and  also  contains  descriptions  of  the  previously  known 
phosphors:  Bologna  stone,  Baldwin's  phosphor,  and 
emerald  phosphor  (green  fluorspar).  See  also  ref.  (113). 


758 


DISCOVERY  OF  THE  ELEMENTS 


that  the  white  solid  mass  left  at  the  bottom  consisted  mainly  of  selenite 
[calcium  sulfate],  and  that  an  acid  passed  over  into  the  receiver.  He 
concluded  that  fluorspar  "consists  principally  of  calcareous  earth  saturated 
with  a  specific  acid"  (79).  By  adding  lime  water  to  a  dilute  solution 
of  this  acid,  he  synthesized  an  artificial  fluorspar  which,  like  the  natural 
mineral,  phosphoresced  when  warmed  in  the  dark. 

Scheele  stated  that  the  acid  of  fluorspar  [hydrofluoric  acid]  can  dis- 
solve siliceous  earth  and  that  therefore  it  is  almost  impossible  to  pre- 
pare the  pure  acid.  He  believed  that  the  earthy  deposit  in  the  receiver 
(Marggrafs  "volatile  earth")  was  siliceous  earth  produced  by  a  reaction 


Johann     Christian     Wiegleb,     1732-1800. 

Pharmacist  and  chemist  of  Langensalza, 
Germany.  Author  of  excellent  books  on 
pharmacy,  chemistry,  and  the  history  of 
chemistry  and  alchemy.  In  his  "Chemical 
Experiments  on  Alkaline  Salts"  (1774), 
he  showed  that  all  of  the  alkali  obtained 
by  the  burning  of  plants  is  pre-existent  in 
them. 


Courtesy  Edgar  Fahs  Smith 


between  the  "acid  of  fluorspar"  and  water.  In  1778  his  friend  Friedrich 
Ehrhart,  a  botanist  at  Hanover  who  had  studied  under  Carl  von  Linn6 
and  T.  Bergman,  wrote  Scheele  that  this  deposit  had  merely  been  dis- 
solved from  the  glass  retort.  When  J.  K.  F.  Meyer  of  Stettin  repeated 
the  experiment,  using  a  lead  retort  instead  of  a  glass  one,  he  found  no 
such  deposit  in  the  receiver  (80).  Carl  Friedrich  Wenzel  (114)  with 
a  lead  retort  and  Giovanni  Antonio  Scopoli  with  a  gold-plated  silver  one 
obtained  similar  results  (76).  In  1781  Johann  Christian  Wiegleb  proved 
quantitatively  that  the  silica  came  from  the  glass  retort,  and  in  the  same 
year  Scheele  became  convinced  of  his  error  (77,  81,  82).  These  results 


THE  HALOGEN  FAMILY  759 


Courtesy  the  Deutsches  Museum  in  Munich 

Carl  Friedrich  Wenzel,  1740-1793.  German  physician  and 
chemist.  Chief  assessor  of  the  Freiberg  mines  and  later 
chemist  at  the  Meissen  porcelain  works.  Author  of  "The 
Doctrine  of  the  Affinity  of  Substances,"  a  work  that  deals 
primarily  with  chemical  proportions.  He  determined 
quantitatively  the  amounts  of  various  acids  necessary  to 
neutralize  given  quantities  of  plant  alkali  ( KOH )  and  mineral 
alkali  (NaOH). 


were  also  confirmed  by  Wilhelm  Heinrich  Sebastian  Bucholtz  (83).  In 
1780  and  again  in  1786  ( the  last  year  of  his  life),  Scheele  published  papers 
defending  his  claim  that  fluorspar  contains  a  peculiar  acid  ( 79 ) . 

The  new  acid  immediately  aroused  widespread  interest,  John  Hill, 
in  the  notes  to  his  translation  of  Theophrastus*  "History  of  Stones/7  stated 
in  1774:  "There  exists  in  the  Mineral  World  a  native  acid;  and  probably 
only  one;  tho7  it  exhibits  itself  under  different  Forms.  Of  the  existence 
of  this  we  are  certain;  altho'  we  never  have  seen  it  pure;  nor  can.  It 
never  becoming  an  Object  of  our  Senses,  but  in  Mixture  with  other  Bodies. 


760 


DISCOVERY  OF  THE  ELEMENTS 


It  has  been  called  the  Vague  Acid  and  the  Universal  Acid.  We  have 
been  accustomed  to  meet  with  it  under  two  distinct  Forms;  and  to  know 
it  under  the  Names  of  two  Species:  These  are  the  Vitriolic  and  the 
Muriatic  Acid:  and  to  these  we  are  lately  taught  to  add  a  third,  which, 
from  the  Place  where  it  has  been  discovered,  Authors  have  called  the 
Swedish  Acid;  and  to  which  some,  tho'  very  improperly,  have  given  the 
Name  of  the  Sparry  Acid.  Perhaps,  in  distinction  from  the  other  two, 
it  may  be  better  named  the  Stony  Acid"  (84,  85,  118). 

In  1786  M.  H.  Klaproth  published  in  Crell's  Annalen  a  method  de- 
vised by  Count  von  Gesler  for  etching  letters  and  drawings  on  glass  with 
hydrofluoric  acid  (76,  86),  and  in  1788  Jean-Pierre-Casimir  de  Marcassus, 


Paulin  Louyet,  1818-1850.  Belgian 
chemist  who  investigated  the  compounds 
of  fluorine.  For  his  attempts  to  liberate 
fluorine,  the  Knox  brothers  placed  at  his 
disposal  their  costly  fluorspar  and  plati- 
num equipment.  His  premature  death 
was  caused  by  continued  exposure  for 
about  a  decade  to  the  toxic  compounds 
of  this  element  (69).  Engraving  by 
Danse,  Brussels,  1851. 


Baron  de  Puymaurin  (1757-1841)  published  a  similar  process  in  the 
Memoir es  de  Toulouse  (87,  88,  89).  The  German  translation  of  Mac- 
quer's  chemical  dictionary,  published  in  1790,  contains  the  following 
detailed  account  of  it  (88). 

"The  acid  of  fluorspar  has  recently  been  used  for  etching  pictures 
on  glass  coated  with  an  etching  ground  through  which  the  picture  is 
etched.  This  art  is  to  a  certain  extent  in  the  process  of  development. 
Klaproth  and  Lichtenberg  among  the  Germans  and  Graf  von  G.  and  M. 
de  Puymaurin  among  the  foreigners  (CrelTs  Beytrage  III,  467  ff )  have 
proposed  it  and  given  instructions.  The  latter  advises  as  the  result  of 
his  experience  that,  first  of  all,  one  must  know  accurately  the  nature  of 
the  glass  to  be  used.  He  observed  that  the  Bohemian,  since  it  is  not 


THE   HALOGEN   FAMILY  761 

homogeneous  and  not  thoroughly  fused,  is  not  acted  on  uniformly  by 
the  acid;  and  that  the  English,  since  it  contains  too  much  lead,  on  which 
the  acid  works  very  fast,  shows  an  unpleasant  spot  wherever  there  is  the 
slightest  break  in  the  varnish  which  serves  as  the  etching  ground.  The 
most  suitable  is  white  mirror-glass,  especially  that  for  small  mirrors.  .  .  . 

"His  best  results  were  obtained  with  a  varnish  consisting  of  equal 
parts  of  mastix  [mastic]  and  a  drying  oil  which  he  had  prepared  by 
heating  linseed  oil  with  red  mercury  cak  in  the  air  apparatus;  but  this 
varnish  could  not  easily  be  applied  as  a  uniform  layer,  and  in  winter  it 
could  not  be  dried  well  without  considerable  heat.  One  applies  it  to 
the  carefully  cleaned  glass,  heated  so  hot  that  one  cannot  hold  one's  hand 
on  it,  by  means  of  little  taffeta  balls  stuffed  with  cotton,  and  then  exposes 
it,  as  the  copper  etchers  do,  to  the  smoke  of  little  resin  candles.  During 
the  etching  the  coated  glass  should  be  laid  on  glass  set  into  a  table- 
leaf  which  can  be  raised  toward  the  light,  so  that  one  can  frequently 
observe  the  etched  lines.  One  etches  the  glass  either  in  demi-relief,  with 
removal  of  the  varnish  between  the  pictures,  or  in  high-relief,  by  letting 
it  remain  in  the  places  where  no  line  of  the  picture  is  to  appear. 

"M.  de  Puymaurin,"  continued  Macquer,  "advises  that  the  acid 
to  be  used  for  etching  be  distilled  from  a  leaden  retort,  at  the  tempera- 
ture of  boiling  water,  from  a  mixture  of  fluorspar  with  four  times  as  much 
vitriolic  acid.  .  .  .  On  the  demi-relief  glass,  one  distributes  the  acid  as 
uniformly  as  possible  with  the  brush,  removes  the  white  crust  when  it 
appears,  pours  on  fresh  acid,  and  repeats  this  process  until  the  picture 
is  etched  deeply  enough.  In  high-relief  pictures,  one  proceeds  as  in  the 
etching  of  copper  plates  with  the  nitric  acid  used  for  parting.  Here,  too, 
the  white  dust  covering  the  etched  lines  gives  evidence  of  the  etching. 
When  it  is  deep  enough,  one  lets  the  acid  flow  off  and  be  kept  for 
future  use. 

"In  this  entire  process,"  said  Macquer,  "one  must  carefully  consider 
the  temperature  of  the  atmosphere.  At  16°  in  the  shade  on  Reaumur's 
thermometer,  one  can  etch  the  picture  on  the  glass  plate,  which  has  been 
coated  and  treated  with  the  acid  in  bright  sunlight,  within  four  or  five 
hours;  in  winter,  however,  one  needs  as  many  days,  and  unless  one  heats 
the  varnish  from  above  with  an  oven,  the  work  cannot  be  done  at  all. 
When  the  picture  is  sufficiently  etched,  and  the  acid  poured  off,  one  washes 
the  glass  a  few  times,  removes  the  varnish  with  coarse  linen  and  alcohol, 
and  finally  rubs  it  with  fine  chalk  dust.  This  etching  of  glass  with  acid 
of  fluorspar  can  also  be  used  for  the  graduation  of  glass  physical  appara- 
tus such  as  eudiometers,  perhaps  also  for  the  plates  for  copying  maps 
and  other  drawings"  (88). 

Baron  de  Puymaurin  also  tested  the  action  of  hydrofluoric  acid  on 
various  kinds  of  stones  placed  in  tin  receptacles.  Stephen  Weston  men- 


762 


DISCOVERY  OF  THE  ELEMENTS 


Fig.  2. 


Kg.  3.          Fig-  *• 


u 


Philosophical  Magazine,  18S6 
Apparatus  Used  by  the  Knox  Brothers  in  Their 
Attempts  to  Liberate  Fluorine.  Upon  treating  dry 
''fluoride  of  mercury"  with  dry  chlorine  they  obtained 
crystals  of  mercuric  chloride.  A  piece  of  gold  foil 
which  had  been  acted  on  by  the  gas  in  the  receiver 
was  placed  on  glass  and  treated  with  sulfuric  acid. 
Since  the  glass  was  attacked,  they  concluded  that 
fluorine  had  been  liberated  and  had  formed  gold 
fluoride.  No  hydrogen  was  detected.  Fig.  1. 
Fluorspar  vessel  in  the  stand  which  holds  down  the 
receiver  by  means  of  spiral  springs.  Fig.  2.  Vessel 
with  cover  off,  showing  the  orifice  and  the  small  de- 
pressions containing  gold  leaf.  Fig.  3.  Receiver. 
Fig.  4.  Stopper. 


tioned  the  hydrofluoric  acid  etchings  of  Puymann  [Puymaurin?]  and 
stated  in  1805  that  "the  best  work  of  this  kind  is  that  which  represents 
Chemistry  weeping  over  the  tomb  of  Scheele,  the  discoverer  of  the 
fluoric  [hydrofluoric]  acid"  (90). 

The  history  of  fluorine  gas  is  a  tragic  record.  Lavoisier,  it  will  be 
recalled,  thought  that  all  acids  contain  oxygen,  but  Sir  Humphry  Davy 
showed  that  "fluoric"  [hydrofluoric]  acid  does  not.  A.-M.  Ampere  sug- 
gested to  Davy  that  it  must  be  a  compound  of  hydrogen  and  an  un- 
known element  (31,  32}.  Paul  Schiitzenberger  expressed  the  belief  that 
this  unknown  substance,  fluorine,  would  be  found  to  be  the  most  active 
of  all  the  elements,  and  correctly  predicted  some  of  its  properties  (18, 19). 
It  is  this  extreme  activity  of  the  element  that  made  its  liberation  such  a 
difficult  and  dangerous  task  and  brought  agony  and  death  to  some  of  the 
pioneer  investigators, 

Davy,  Gay-Lussac,  and  Thenard  all  suffered  intensely  from  the 
effects  of  inhaling  small  quantities  of  hydrogen  fluoride.  Davy  found 


THE   HALOGEN   FAMILY  763 

that  his  silver  and  platinum  containers  were  attacked,  but  believed  that 
fluorine  could  be  liberated  if  a  fluorspar  vessel  were  used  (23,  30,  62}. 
Two  members  of  the  Royal  Irish  Academy,  George  Knox  and  his  brother, 
the  Reverend  Thomas  Knox,  of  Toomavara,  Tipperary,  made  an  ingenious 
apparatus  of  fluorspar.  They  were  unable,  however,  to  collect  and  study 
the  gas.  Both  suffered  the  frightful  torture  of  hydrofluoric  acid  poison- 
ing (20).  The  Reverend  Thomas  Knox  nearly  lost  his  life,  and  George 
Knox  had  to  rest  in  Naples  for  three  years  in  order  to  regain  his  health 
(40).  P.  Louyet  of  Brussels,  although  fully  aware  of  the  Knox  brothers' 
misfortune,  continued  his  dangerous  researches  too  long,  and  died  a  martyr 
to  science  (17,  18,  40,  42).  Professor  Jerome  Nickles  of  Nancy  met  a 
similar  fate  (35,  43,  60,  67). 


Edmond  Fremy,  1814-1894.  Professor 
of  chemistry  at  the  Ecole  Polytechnique 
and  director  of  the  Museum  d'Histoire 
Naturelle.  He  electrolyzed  anhydrous 
calcium  fluoride  but  could  not  collect 
the  fluorine.  He  was  present,  however, 
when  his  former  pupil,  Henri  Moissan, 
exhibited  the  new  gas  before  a  com- 
mittee from  the  Academy  of  Sciences. 
Fremy  wrote  a  monograph  on  the  syn- 
thesis of  rubies.  See  /.  Chem.  Educ., 
8,  1017-19  (June,  1931)  f or  illustrations 
of  his  artificial  rubies. 


Edmond  Fremy,  who  had  watched  Louyet  perform  some  of  his  ex- 
periments (33),  tried  to  decompose  anhydrous  calcium  fluoride  electro- 
lytically,  and  did  obtain  calcium  at  the  cathode,  while  a  gas,  which  must 
have  been  fluorine,  escaped  at  the  anode  (34).  However,  because  of 
its  tendency  to  add  on  to  other  substances  and  form  ternary  and  quater- 
nary compounds,  Fremy  failed  in  all  his  attempts  to  collect  and  identify 
the  gas.  When  he  allowed  chlorine  to  act  on  a  fluoride,  he  obtained  no 
fluorine,  but  only  a  fluochloride;  when  he  used  oxygen  in  place  of  chlo- 
rine, he  obtained  an  oxyfluoride. 

This  seemingly  hopeless  field  of  experimentation  was  soon  aban- 
doned, but  in  1869  the  English  chemist  George  Gore  liberated  a  little 
fluorine,  which  immediately  combined  explosively  with  hydrogen  (IS, 


764  DISCOVERY  OF  THE  ELEMENTS 

35).  When  he  tried  to  electrolyze  anhydrous  hydrofluoric  acid  "with 
anodes  of  gas-carbon,  carbon  of  lignum-vitae,  and  of  many  other  kinds 
of  wood,  of  palladium,  platinum,  and  gold,  .  .  .  the  gas-carbon  disinte- 
grated rapidly,  all  the  kinds  of  charcoal  flew  to  pieces  quickly,  and  the 
anodes  of  palladium,  platinum,  and  gold  were  corroded  without  evolu- 
tion of  gas"  (35).  Moissan  mentioned  the  "remarkable  exactitude"  of 
Gore's  memoir  (-23). 

The  apparently  impossible  task  was  finally  accomplished  by  Moissan 
in  1886.  Ferdinand-Frederic-Henri  Moissan  was  born  at  5  Rue  Mon- 
tholon  in  Paris  on  September  28,  1852.  When  he  was  twelve  years  old, 
the  family  moved  to  the  little  town  of  Meaux  in  the  department  of  Seine-et- 
Marne,  where  he  attended  the  municipal  college.  His  first  lessons  in 
chemistry  were  received  from  his  father,  a  railroad  official  (22,  58). 

Obliged  to  leave  school  at  the  age  of  eighteen  years,  he  became  an 
apprentice  in  the  Bandry  apothecary  shop  located  at  the  intersection  of 
Rue  Pernelle  and  Rue  Saint  Denis  in  Paris.  Here  his  ready  knowledge  of 
chemistry  enabled  him  to  save  the  life  of  a  man  who  had  swallowed  arsenic 
in  an  attempt  at  suicide  (21,  22).  In  1872  Moissan  decided  to  give  up  his 
position  at  the  pharmacy  in  order  to  study  under  Edmond  Fremy  at  the 
Musee  d'Histoire  Naturelle.  Here  he  not  only  made  rapid  progress  in 
chemistry  and  pharmacy,  but  also  became  a  connoisseur  of  art  and  litera- 


Dr.  George  Gore,*  1826-1908.  English 
electrochemist  Head  of  the  Institute  of 
Scientific  Research,  Easy  Row,  Birming- 
ham. He  improved  the  art  of  electroplat- 
ing and  wrote  treatises  on  "The  Art  of 
Electrometallurgy"  and  "The  Electrolytic 
Separation  and  Refining  of  Metals."  His 
estate  was  bequeathed  to  the  Royal 
Society  of  London  and  the  Royal  Institu- 
tion of  Great  Britain. 


*  This  portrait  was  obtained  through  the  courtesy  of  Mr.  R.  B.  Pilcher,  Registrar  and 
Secretary  of  the  Institute  of  Chemistry  of  Great  Britain  and  Ireland, 


THE  HALOGEN   FAMILY 


765 


Professor  Moissan  Preparing  Fluorine  in  His  Laboratory  at  the  ficole  de 
Pharmacie  in  Paris* 

ture,  and  even  wrote  a  rhymed  play  which  was  almost  accepted  for  the 
audiences  at  the  Odeon.  He  was  afterward  able  to  laugh  at  this  early 
disappointment  and  to  say,  "I  believe  I  did  better  to  study  chem- 
istry"* (22). 

In  1879  he  passed  his  examination  for  first-class  pharmacist  and  ac- 
cepted a  position  at  the  ficole  Superieure  de  Pharmacie  (21,  58). 

Three  years  later  there  occurred  in  Moissan's  life  a  most  fortunate 
event— his  marriage  to  Leonie  Lugan.  She  proved  to  be  a  devoted  wife 
and  comrade,  a  hospitable,  charming  hostess,  and  a  great  help  to  him  in 
his  scientific  work.  M.  Lugan  was  also  an  ideal  father-in-law,  in  full  sym- 
pathy with  Moissan's  scientific  researches.  He  gladly  provided  material 
support  for  his  daughter's  family,  and  urged  Moissan  to  devote  all  his 
time  to  science,  unhampered  by  financial  worries.  Since  the  latter  had 
no  laboratory  at  the  School  of  Pharmacy,  he  did  his  first  experimental 
work  in  a  building  situated  on  the  Rue  Lancry,  but  J.-H.  Debray  after- 
ward allowed  him  to  use  the  more  powerful  battery  in  a  temporary  bar- 
racks on  the  Rue  Michelet  (22}. 

*  The  picture  of  Moissan  preparing  fluorine  has  been  reproduced  from  an  article 
by  Gaston  Tissandier,  La  Nature,  18,  [1],  177  (Feb.  22,  1890),  by  permission  of 
Masson  et  Cie.,  Editeurs,  Paris.- 

t  "Je  crois  que  f ai  mieux  fait  de  faire  de  la  chimie." 


766  DISCOVERY  OF  THE  ELEMENTS 

Fremy  had  concluded  from  his  experiments  that  fluorine  had  prob- 
ably been  liberated  in  the  electrolysis  of  the  fluorides  of  calcium,  potas- 
sium, and  silver,  but  that,  because  the  temperature  had  been  too  high,  it 
had  immediately  attacked  the  container.  He  prepared  anhydrous  hydro- 
gen fluoride,  but  found  himself  caught  in  the  horns  of  the  following 
dilemma:  when  moist  hydrogen  fluoride  was  electrolyzed,  he  obtained 
only  hydrogen,  oxygen,  and  ozone;  and  dry  hydrogen  fluoride  would  not 
conduct  the  current  (22). 

Moissan  reasoned  that  if  he  were  trying  to  liberate  chlorine  he  would 
not  choose  a  stable  solid  like  sodium  chloride,  but  a  volatile  compound 
like  hydrochloric  acid  or  phosphorus  pentachloride.  His  preliminary 
experiments  with  silicon  fluoride  convinced  him  that  this  was  a  very  stable 
compound,  and  that,  if  he  should  ever  succeed  in  isolating  fluorine,  it 
would  unite  with  silicon  with  incandescence,  and  that  therefore  he  might 
use  silicon  in  testing  for  the  new  halogen.  After  many  unsuccessful 
attempts  to  electrolyze  phosphorus  trifluoride  and  arsenic  trifluoride, 
and  after  four  interruptions  caused  by  serious  poisoning,  he  finally  ob- 
tained powdered  arsenic  at  the  cathode  and  some  gas  bubbles  at  the  anode. 
However,  before  these  fluorine  bubbles  could  reach  the  surface,  they 
were  absorbed  by  the  arsenic  trifluoride  to  form  pentafluoride  (18,  23). 

Moissan  finally  used  as  electrolyte  a  solution  of  dry  potassium  acid 
fluoride  in  anhydrous  hydrofluoric  acid.  His  apparatus  consisted  of  two 
platinum-iridium  electrodes  sealed  into  a  platinum  U-tube  closed  with 
fluorspar  screw  caps  covered  with  a  layer  of  gum  lac  ( 42,  49,  59 ) .  The 
U-tube  was  chilled  with  methyl  chloride,  the  gas  now  used  in  many 
modern  refrigerators,  to  a  temperature  of  —23°. 

Success  finally  came.  On  June  26,  1886,  a  gas  appeared  at  the  anode, 
and  when  he  tested  it  with  silicon,  it  immediately  burst  into  flame.  Two 
days  later  he  made  the  following  conservative  announcement  to  the 
Academy: 

One  can  indeed  make  various  hypotheses  on  the  nature  of  the  liberated 
gas;  the  simplest  would  be  that  we  are  in  the  presence  of  fluorine,  but  it  would 
be  possible,  of  course,  that  it  might  be  a  perfluoride  of  hydrogen  or  even  a 
mixture  of  hydrofluoric  acid  and  ozone  sufficiently  active  to  explain  such  vigor- 
ous -action  as  this  gas  exerts  on  crystalline  silicon  (42) . 

This  announcement  was  read  to  the  Academy  by  Debray,  for  Moissan 
was  not  then  a  member,  and  the  president  appointed  a  committee  con- 
sisting of  MM.  J.-H.  Debray,  Marcelin  Berthelot,  and  Edmond  Fremy  to 
investigate  the  discovery.  In  the  presence  of  these  distinguished  guests, 
the  apparatus  acted  like  a  spoiled  child.  Moissan  could  not  obtain  as 
much  as  a  bubble  of  fluorine.  However,  on  the  following  day  he  used 
fresh  materials  and  demonstrated  his  discovery  to  the  entire  satisfaction  of 


THE  HALOGEN   FAMILY 


767 


Pierre-Eugene-Marcelin  Berthelot,  1827-1907.  French  chemist  and 
historian  of  chemistry.  His  researches  were  in  the  diverse  fields  of 
organic  synthesis,  chemical  statics  and  dynamics,  thermochemistry,  ex- 
plosives, nitrifying  bacteria  in  the  soil,  and  the  oriental  sources  of  alchemy. 
In  his  early  days  he  assisted  Balard  at  the  College  de  France  and  many 
years  later  he  served  on  a  committee  with  Debray  and  Fremy  to  investi- 
gate Moissan's  discovery  of  fluorine.  See  also  refs.  (115)  and  (116}. 


768  DISCOVERY  OF  THE  ELEMENTS 

the  committee  (22).  Thus  Fremy,  who  had  come  so  near  to  making  this 
discovery  himself,  was  able  to  say  with  all  sincerity,  "A  professor  is  always 
happy  when  he  sees  one  of  his  students  proceed  farther  and  higher  than 
himself"  (60). 

The  successful  isolation  of  fluorine  made  Moissan's  name  known 
throughout  the  scientific  world,  and  in  1893  another  achievement  won  for 
him  more  popular  publicity  than  he  desired.  On  February  sixth  of  that 
year  he  apparently  succeeded  in  preparing  small  artificial  diamonds  by 
subjecting  sugar  charcoal  to  enormous  pressure  (52,  53,  63).  Most  of 
his  diamonds  were  black  like  carbonado,  but  the  largest  one,  0.7  of  a 


Alfred  E.  Stock.  Former  director  of 
the  Chemical  Institute  of  the  Tech- 
nische  Hochschule  of  Karlsruhe. 
Former  student  of  Henri  Moissan  and 
author  of  an  excellent  biographical 
sketch  of  him.  Visiting  lecturer  at 
Cornell  University  in  1932.  He  is  an 
authority  on  the  high-vacuum  method 
for  studying  volatile  substances,  the 
chemistry  of  boron,  the  preparation 
and  properties  of  beryllium,  and 
chronic  mercurial  poisoning. 


millimeter  long,  was  colorless.  His  colleagues  affectionately  named  this 
little  diamond  "The  Regent,"  for  to  them  it  was  as  precious  as  the  137- 
carat  specimen  in  the  Louvre  (22).  Recent  experimenters,  however,  have 
expressed  doubt  that  Moissan's  products  were  genuine  diamonds  (169). 
Moissan's  electric  furnace  was  a  valuable  incentive  to  research.  With 
its  aid  he  prepared  many  uncommon  metals  such  as  uranium,  tungsten 
(wolfram),  vanadium,  chromium,  manganese,  titanium,  molybdenum, 
columbium  (niobium),  tantalum,  and  thorium,  much  of  this  work  being 
done  at  the  Edison  Works  on  Avenue  Trudaine  (24,  61).  As  a  practical 


THE  HALOGEN  FAMILY  769 

result  of  her  husband's  researches,  Mme.  Moissan  was  one  of  the  first 
women  in  the  world  to  use  aluminum  cooking  utensils  (22). 

Moissan  always  insisted  on  extreme  neatness  in  his  laboratory,  and 
the  wooden  floors  were  waxed  every  Saturday.  Alfred  Stock  (64)  relates 
that  one  day  Professor  Moissan  looked  critically  at  the  floor  and  said 
reproachfully,  "Who  did  that?"  Upon  careful  examination,  Dr.  Stock 
noticed  that  a  few  drops  of  water  from  the  tip  of  his  wash-bottle  had 
fallen  to  the  waxed  floor  (22). 


Henri  Moissan,  1852-1907.  Professor 
of  chemistry  at  the  Ecole  Superieure 
de  Pharmacie.  The  discoverer  of  the 
element  fluorine.  With  his  electric 
furnace  he  prepared  many  uncommon 
metals  such  as  uranium,  tungsten 
(wolfram),  and  vanadium. 


Moissan  was  one  of  the  most  polished  scientific  lecturers  in  Paris. 
His  ease  of  delivery,  his  well-modulated  voice,  his  carefully  chosen  ex- 
periments, and  his  gentle  humor  attracted  great  crowds  to  his  lectures  at 
the  Sorbonne.  At  exactly  five  o'clock  the  two  large  doors  of  the  lecture 
room  used  to  be  opened  simultaneously  by  two  servants,  and  at  a  quarter 
past  five  the  lecture  began.  Then  for  an  hour  and  a  quarter  Moissan 
held  the  eager  attention  of  his  audience.  Sir  William  Ramsay  said  of  him, 

His  command  of  language  was  admirable;  it  was  French  at  its  best.  The 
charm  of  his  personality  and  his  evident  joy  in  exposition  gave  keen  pleasure  to 
his  auditors.  He  will  live  long  in  the  memories  of  all  who  were  privileged  to 
know  him,  as  a  man  full  of  human  kindness,  of  tact,  and  of  true  love  for  the 
subject  which  he  adorned  by  his  life  and  work  (22,  48) . 

Moissan  had  an  artistic,  hospitable  home  in  the  quiet  Rue  Vauquelin, 
and  was  proud  of  his  Corot  landscape  and  his  fine  collection  of  auto- 


770  DISCOVERY  OF  THE  ELEMENTS 

graphs.  M.  and  Mme.  Moissan  and  their  son  Louis  usually  spent  their 
vacations  traveling  in  Italy,  Spain,  Greece,  the  Alps,  or  the  Pyrenees, 
and  in  1904  Moissan  came  to  America  to  visit  the  St.  Louis  World's 
Fair  (22). 

His  life  was  undoubtedly  shortened  by  his  continued  work  with  the 
toxic  gases,  fluorine  and  carbon  monoxide.  He  died  on  February  20, 
1907.  His  only  child,  Louis,  an  assistant  at  the  ficole  de  Pharmacie,  who 
was  killed  on  a  battlefield  of  World  War  I,  left  200,000  francs  to  the 
school  for  the  establishment  of  two  prizes:  the  Moissan  chemistry  prize 
in  memory  of  his  father  and  the  Lugan  pharmacy  prize  in  honor  of  his 
mother  (25,  65). 

Other  Sources  of  Fluorine.  M.  H.  Klaproth  discovered  that  cryolite, 
the  mineral  which  later  came  to  be  used  as  a  flux  in  the  industrial  electro- 
lytic production  of  aluminum,  is  a  fluoride  of  sodium  and  aluminum  (76). 
In  1878  S.  L.  Penfield,  in  a  research  consisting  of  eight  analyses  of 
amblygonite,  proved  that,  contrary  to  the  views  of  Carl  Friedrich 
Rammelsberg,  fluorine  and  hydroxyl  can  replace  each  other  in  the  same 
mineral  (155).  Traces  of  fluorine  are  found  in  all  types  of  natural  water: 
in  oceans,  lakes,  rivers,  and  springs  (156). 

Fluorine  in  Plants  and  Animals.  In  1802  Domenico  Pini  Morichini 
discovered  the  presence  of  fluorine  in  fossil  ivory  (157).  He  later  de- 
tected it  in  the  enamel  of  the  teeth,  and  Berzelius  soon  confirmed  the 
discovery  and  showed  that  fluorine  is  also  a  normal  constituent  of  bone 
(158, 159, 165).  The  presence  of  excessive  amounts  of  fluoride  in  drink- 
ing water  causes  the  well-known  mottling  of  the  enamel  of  children's 
teeth  (160),  but  small  amounts  of  fluoride  protect  the  teeth  from  dental 
caries  (161). 

J.  D.  Dana  showed  that  fluorine  occurs  in  the  lime  of  corals  (162). 
Dr.  G.  Wilson  of  Edinburgh  and  J.  G.  Forchhammer  both  detected  it 
directly  in  sea  water  from  the  Sound  near  Copenhagen,  and  the  latter 
demonstrated  it  still  more  easily  in  the  boiler  scale  from  Transatlantic 
steamers  (98). 

In  1857  Jerome  Nickles  demonstrated  the  presence  of  fluorine  in 
the  blood  of  many  mammals  and  birds.  In  disagreement  with  Berzelius, 
he  regarded  the  fluorine  in  bones  as  an  essential  ingredient.  "Fluorine," 
said  Nickles,  "exists  in  the  bile,  in  the  albumen  of  the  egg,  in  gelatine, 
in  urine,  in  saliva,  in  hair;  in  a  word,  the  animal  organism  is  penetrated 
by  fluorine,  and  it  may  be  expected  to  be  found  in  all  the  liquids  which 
impregnate  it"  (163). 

Armand  Gautier  and  Paul  Clausmann  found  fluorine  to  be  a  uni- 
versal accompaniment  of  phosphorus  in  plant  tissues  (164).  Although 
the  unconditional  necessity  for  fluorine  for  the  plant  has  not  been  proved, 
it  does  occur  in  all  plants  and  all  plant  parts  (167). 


THE  HALOGEN  FAMILY  771 

LITERATURE  CITED 

1 I )  MOISSAN,  H.,  "Le  Fluor  et  ses  Composes/'  Steinheil,  Paris,  1900,  preface,  p, 

viii. 

(2)  OSWALD,  M.,  "L'iDvolution  de  la  chimie  au  XIX6  Siecle,"  Bibliotheque  La- 

rousse,  Paris,  1913,  p.  26.     Quotation  from  Balard. 

(3)  Alembic  Reprint  No.  13,  "The  Early  History  of  Chlorine/'  University  of  Chi- 

cago Press,  Chicago,  1902,  pp.  8-9;  C.  W.  SCHEELE,  "On  manganese  and  its 
properties." 

(4)  Ibid.,  p.  20.    C.-L.  BERTHOLLET,  "Memoir  on  Dephlogisticated  Marine  Acid," 

Memoires  de  FAcademie  Royale,  1785,  Paris,  1788,  pp.  276-95. 

(5)  FARBER,  E.  "Geschichtliche  Entwicklung  der  Chemie,"  Springer,  Berlin,  1921, 

pp.  119-22. 

(6)  Alembic  Reprint  No.  13,  Ref.  (3),  pp.  37-48.     L.-J.  GAY-LUSSAC  and  L.-J. 

THENARD,  "On  the  nature  and  properties  of  muriatic  acid  and  of  oxygenated, 
muriatic  acid." 

(7)  Ibid.,  p.  49.    L.-J.  GAY-LUSSAC  and  L.-J.  THENARD,  "Extract  from  'Recherches 

Physico-Chimiques/ "  Vol.  2,  Imprimerie  de  Crapelet,  Paris,  1811,  p.  262. 

(8)  JAGNAUX,  R.,.  "Histoire  de  la  Chimie,"  Vol.  1,  Baudry  et  Cie.,  Paris,  1891,  pp. 

505-13. 

(9)  THOMSON,  THOMAS,  "History  of  Chemistry,"  Vol.  2,  Colburn  and  Bentley, 

London,  1831,  p.  268;  J.  DAVY,  "The  Collected  works  of  Sir  Humphry 
Davy,  Bart.,"  Vol.  1,  Smith,  Elder  and  Co.,  London,  1839,  p.  123. 

(10)  A.  W.  H.,  "Zur  Erinnerung  an  Friedrich  Wohler,"  Ber.,  15,  3127-290  (Part 

2,  1882). 

(11 )  OSWALD,  M.,  "L7£volution  de  la  Chimie  au  XIXe  Siecle,"  Ref.  (2),  pp.  22-6. 

(12)  JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  Ref.  (8),  Vol.  1,  pp.  521-8. 

(13)  TORAUDE,  L.-G.,  "Bernard  Courtois  et  la  Decouverte  de  llode,"  Vigot  Freres, 

Paris,  1921,  164  pp. 

(14)  HOEFER,   F.,   "Nouvelle   Biographic   Generale,"   Didot   Freres,   Paris,    1866. 

Article  on  Ballard  (sic). 

( 15)  SODERBAUM,  H.  G.,  "Jac.  Berzelius  Bref,"  Vol.  2,  part  4,  Almqvist  and  Wiksells, 

Upsala,  1912-1914,  p.  67. 

(16)  BALARD,  A.-J.,  "Memoir  on  a  peculiar  substance  contained  in  sea  water," 

Annals  of  Phil,  [1],  28,  381-7  (Nov.,  1826);  411-24  (Dec.,  1826) 

(17)  OSWALD,  M.,  "L'Evolution  de  la  Chimie  au  XIXe  Siecle,"  Ref.  (2),  pp.  28-30. 

(18)  JAGNAUX,  R.,  "Histoire  de  la  Chimie,"  Ref.  ( 8 ) ,  Vol.  1,  pp.  528-49. 

(19)  MOISSAN,  H.,  "Le  Fluor  et  ses  Composes,"  Ref.  (1 ),  pp.  8-9. 

(50)  KNOX,  G.  J.  and  the  REV.  THOMAS  KNOX.  "On  fluorine,"  Phil  Mag.,  [3].  9, 
107-9  (Aug.,  1836);  [3],  12,  105-6  (Jan.,  1838);  G.  J.  KNOX,  "Researches 
on  fluorine,"  ibid.,  [3],  16,  192-4  (Mar.,  1840). 

(21)  HARROW,  B.,  "Eminent  Chemists  of  Our  Time,"  D.  Van  Nostrand  Co.,  New 

York  City,  1920,  p.  138. 

(22)  STOCK,  A.,  "Henri  Moissan,"  Ber.,  40,  5099-130  (Band  4,  1907). 

(23)  MOISSAN,  H.,  "Le  Fluor  et  ses  Composes,"  Ref.  ( 1 ),  pp.  1-36. 

(24)  HARROW,  B.,  "Eminent  Chemists  of  Our  Time,"  Ref.  (21 ),  p.  148. 

(25)  Ibid.,  p.  153. 

(26)  ANGLADA,  Letter  to  the  editors,  Ann.  chim.  phys.,  [2],  33,  222-3  ( 1826). 

(27)  LIEBIG,  J.,  "Sur  le  brome,"  Ann.  chim.  phys.,  [2],  33,  330-3  (1826). 

(28)  BALARD,  A.-J.,  "Memoire  sur  une  substance  particuliere  contenue  dans  Teau  de 

la  mer,"  Ann.  chim.  phys.,  [2],  32,  337-81  (1826). 

(29)  VAUQUELIN,  N.-L.,  L.-J.  THENARD,  and  L.-J,  GAY-LUSSAC,  "Rapport  sur  le 

memoire  de  M.  Balard  relatif  a  une  nouvelle  substance,"  Ann.  chim.  phys., 
[2],  32,  382-4  (1826);  Annals  of  Phil,  [1],  28,  425-6  (Dec.,  1826). 

(30)  DAVY,  H.,  "An  account  of  some  new  experiments  on  the  fluoric  compounds; 

with  some  observations  on  other  objects  of  chemical  inquiry,"  Phil.  Trans., 
104,62-73  (1814)  . 


772  DISCOVERY  OF  THE  ELEMENTS 

(SI )     DAVY,  H.,  "Some  experiments  and  observations  on  the  substances  produced  in 
different   chemical   processes    on   fluor   spar/'   Phil    Trans.,    103,   263-79 

(1813).  .  „ 

(32)  AMPERE,  A.-M,  "Suite  dune  classification  naturelle  pour  les  corps  simples, 

Ann.  chim.  phys.,  [2],  2,  19-25  (May,  1816). 

(33)  FREMY,  E.,  "Recherches  sur  les  fluorures,"  Compt.  rend.,  38,  393-7  (teb.  27, 

(34)  FREMY,  E.,  Decomposition  des  fluorures  au  moyen  de  la  pile,"  Compt.  rend., 

40,  966-8  (Apr.  23,  1855). 

(35)  GORE,  G.,  "On  hydrofluoric  acid,"  Chem.  News,  19,  74-5  (Feb.  12,  1869); 

/.  Chem.  Soc.,  Trans.,  22,  368-406  (1869);  Phil  Trans.,  159,  173  (1869). 

(36)  SMITH,  E.  F.,  "Bromine  and  its  discoverers,  1826-1926,"  /.  Chem.  Educ.,  3, 

382-4  (Apr.,  1926). 

(37)  WEHELE,  "Geschichte  der  Salzsaure,"  Carl  Gerold,  Vienna,  1819,  pp.  83-4. 

(38)  HENRY,  W.,  "Account  of  a  series  of  experiments,  undertaken  with  the  view  of 

decomposing  the  muriatic  acid,"  Phil.  Trans.,  90,  188-203  (1800). 

( 39 )  GAY-LUSSAC,  L.-J.,  "Untersuchungen  iiber  das  Jod,"  Ostwald's  Klassiker,  No.  4. 

Wittielm  Engelmann,  Leipzig,  1889,  52  pp.;  Ann.  chim.  phys.,  [I],  91, 
5-160(1813). 

(40)  LOXJYET,  P.,  "Nouvelles  recherches  sur  I'isolement  du  fluor,  la  composition  des 

fluorures,  et  le  poids  atomique  du  fluor,"  Compt.  rend.,  23,  960-8  ( Nov.  23, 
1846);  Ann.,  64,  239-40  (Heft  2,  1848);  "De  la  veritable  nature  de  1'acide 
fluorhydrique  anhydre,"  Compt.  rend.,  24,  434-6  (Mar.  15,  1847). 

(41 )  BALDWIN,  R.  T.,  "History  of  the  chlorine  industry/'  /.  Chem.  Educ.,  4,  313-9 

(Mar,  1927). 

(42)  MOISSAN,   H.,   "Action   d'un  courant   electrique   sur   1'acide  fluorhydrique. 

Compt.  rend.,  102,  1543-4  (June  28,  1886);  103,  202-5  (July  19,  1886); 
256-8  (July  26,  1886);  Ann.  chim.  phys.,  [6],  12,  472-537  (Dec,  1887); 
Chem.  News,  54,  51  (July  30,  1886);  80  (Aug.  13,  1886). 

(43)  NICKLES,  J,  "Recherche  du  fluor.     Action  des  acides  sur  le  verre,"  Compt. 

rend.,  44,  679-81  (Mar.  30,  1857). 

(44)  BALARD,  A.-J,  "Recherches  sur  la  nature  des  combinaisons  decolorantes  du 

chlore,"  Ann.  chim.  phys.,  [2],  57,  225-304  ( 1834). 

(45)  CLEMENT,  N.  and  C.-B.  DESORMES,  "Decouverte  d'une  substance  nouvelle 

dans  le  Vareck  par  M.  B.  Courtois,"  Ann.  chim.  phys.,  [1],  88,  304-10 
(1813). 

(46)  "Lettre  de  M.  Humphry  Davy  sur  la  nouvelle  substance  decouverte  par  M. 

Courtois  dans  le  sel  de  Vareck,"  Ann.  chim.  phys.,  [1],  88,  322-9  ( 1813). 

(47)  Obituary  of  Bakrd,  J.  Chem.  Soc.,  Abstr.,  31,  512-14  ( 1877). 

(48)  RAMSAY,  W,  "Moissan  memorial  lecture,"  J.  Chem.  Soc.,  Trans.,  101,  477-88 

(Part  1,  1912);  "Chemical  Society  Memorial  Lectures,  1901-1913,"  Vol.  2, 
Gurney  and  Jackson,  London,  1914,  pp.  189-98. 

(49)  TISSANDIER,  G,  "Le fluor,"  La  Nature,  18,  [1],  177-9  (Feb.  22,  1890). 

(50)  DAVY,  DR.  JOHN,  "The  Collected  Works  of  Sir  Humphry  Davy,  Bart,"  Vol.  1, 

•Smith,  Elder  and  Co,  London,  1839,  p.  400. 

(51 )  TORAUDE,  L.-G,  "Bernard  Courtois  et  la  Decouverte  de  llode,"  Ref.  (13),  pp. 

41-2. 

(52)  "Classics  of  science:   Moissan's  artificial  diamonds,"  Sci.  News  Letter,   14, 

99-100  (Aug.  18,  1928). 

( 53)  MOISSAN,  H,  "The  Electric  Furnace,"  English  translation  by  Lenher,  Chemical 

Publishing  Co,  Easton,  Pa,  1904,  305  pp. 

(54)  TORAUDE,  L.-G,  "Bernard  Courtois,"  Ref.  (13),  p.  59. 

(55)  Ibid.,  pp.  64-5. 

(56)  STTEGLITZ,  J,  "Chemistry  in  Medicine,"  The  Chemical  Foundation  Inc,  New 

York  City,  1928,  pp.  272-96.  Article  by  Dr.  David  Marine  on  "Iodine  in 
the  prevention  and  treatment  of  goiter." 


THE   HALOGEN   FAMILY  773 

(57)  LANDOLT,  H.,  "Carl  Lowig/'  Ber.,  23,  1013  (Part  1,  1890);  905-9  (Part  3, 

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Courtesy  Lady  Ramsay 

Sir  William  Ramsay,  1852-1916.  Scottish  chemist  and  physi- 
cist. Discoverer  of  the  inert  gases.  Lord  Rayleigh  was  a  co- 
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discovered  radon,  or  radium  emanation,  Ramsay  and  Whitlaw 
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member  of  the  argon  family. 


Accurate  and  minute  measurement  seems  to  the  non- 
scientific  imagination  a  less  lofty  and  dignified  work 
than  looking  for  something  new.  But  nearly  all  the 
grandest  discoveries  of  science  have  been  but  the 
rewards  of  accurate  measurement  and  patient  long- 
continued  labor  in  the  minute  sifting  of  numerical 
results  (1). 


28 

The  inert  gases 


In  1894  Lord  Rayleigh  and  Sir  William  Ramsay  startled  the  sci- 
entific world  by  announcing  the  discovery  of  a  new  elementary, 
gaseous  constituent  of  the  atmosphere.  Thorough  investigation 
of  the  properties  of  the  new  element,  which  they  called  argon, 
has  shown  that  it  has  scarcely  any  tendency  whatsoever  to  form 
chemical  compounds.  Another  closely  related  gas  was  revealed 
in  a  manner  no  less  dramatic.  In  1868  the  astronomers  Jules 
Janssen  and  Sir  Norman  Lockyer  had  independently  observed  in 
the  suns  spectrum  a  yellow  line,  D5,  which  did  not  belong  to 
any  element  then  known  to  exist  on  the  earth,  and  Lockyer  had 
therefore  postulated  the  existence  of  a  solar  element,  helium. 
In  1895  Ramsay  in  England  and  Cleve  and  Langlet  in  Sweden 
independently  discovered  helium  in  a  radioactive  mineral.  The 
researches  of  Ramsay  and  Travers  soon  revealed  three  other 
gases,  neon,  krypton,  and  xenon,  which,  since  they  show  almost 
no  tendency  to  unite  with  other  elements,  are  classified  with 
argon  and  helium  in  the  aristocratic  family  of  the  noble  gases.9 
Radon,  the  heaviest  member  of  the  group,  will  be  discussed  in 
Chapter  29  with  the  natural  radioactive  elements. 

C/  ntil  the  closing  years  of  the  nineteenth  century  chemists 
believed  that  the  atmosphere  had  been  thoroughly  investigated,  and  no 
one  thought  for  a  moment  of  searching  there  for  new  elements.  It  is  true 
however,  that  Mr.  Henry  Cavendish  had  long  before  predicted  the  dis- 
covery of  an  unknown  gas  in  the  atmosphere,  for  in  1785  he  had  passed 
electric  sparks  through  a  mixture  of  oxygen  and  common  air  in  the 
presence  of  alkali  ("soap-lees"),  and  had  found  that  part  of  the  "phlogisti- 
cated  air"  (nitrogen )  had  failed  to  be  oxidized  and  absorbed.  He  had  said 
that  this  residue  was  "certainly  not  more  than  Viao  of  the  bulk  of  the 
phlogisticated  air  let  up  into  the  tube';  so  that  if  there  is  any  part  of  the 
phlogisticated  air  of  our  atmosphere  which  differs  from  the  rest  and 
cannot  be  reduced  to  nitrous  acid,  we  may  safely  conclude  that  it  is  not 
more  than  Viao  part  of  the  whole"  (2).  This  important  experiment  had 

*  A  few  compounds  of  the  elements  of  this  group  have  been  reported  in  chemical 
literature. 

779 


780 


DISCOVERY  OF  THE  ELEMENTS 


long  been  forgotten  by  chemists,  but  in  1882  Lord  Rayleigh  began  a 
research  on  the  densities  of  the  gases  in  the  atmosphere. 

John  William  Strutt,  the  third  Lord  Rayleigh,  was  born  at  Terling  on 
November  12,  1842.  His  ability  for  clear  thinking  and  self-expression  was 
evident  in  his  student  days,  and  when  he  was  Senior  Wrangler  in  the 
Tripos  in  1865,  one  of  his  examiners  remarked,  "Strutfs  papers  were  so 
good  that  they  could  have  been  sent  straight  to  press  without  revision" 
(41). 


John  William  Strutt,  the  Third 
Lord     Rayleigh,     1842-1919. 

Professor  of  physics  at  Caven- 
dish Laboratory,  Cambridge. 
He  made  elaborate  investiga- 
tions of  the  electrochemical 
equivalent  of  silver  and  of  the 
combining  volumes  and  com- 
pressibilities of  gases.  His  ob- 
servation that  nitrogen  pre- 
pared from  the  atmosphere  is 
heavier  than  nitrogen  pre- 
pared from  ammonia  led  to 
the  discovery  of  argon,  the  first 
noble  gas.  He  also  con- 
tributed to  optics  and  acous- 
tics. 


Courtesy  of  L.  C.  Newell 


After  the  great  physicist  Clerk  Maxwell  died  in  1879,  Lord  Rayleigh 
became  his  successor  at  the  Cavendish  Laboratory,  Cambridge.  During 
his  professorship  the  classes  increased  in  size,  and  women  from  Girton 
and  Newnham  colleges  were  for  the  first  time  admitted  on  the  same  terms 
as  the  men.  Since  he  was  allowed  insufficient  funds  for  the  purchase  of 
new  apparatus,  he  contributed  £500  of  his  own  money  and  solicited  his 
friends  for  similar  contributions  until  he  had  collected  £  1500  (3). 

In  1882  Lord  Rayleigh  told  the  British  Association  that  he  had  begun 
an  investigation  of  the  densities  of  hydrogen  and  oxygen  to  find  out 
whether  or  not  the  ratio  is  exactly  1  to  16  in  accordance  with  William 


THE  INERT   GASES  781 

Front's  hypothesis  that  all  atomic  weights  are  multiples  of  the  atomic 
weight  of  hydrogen;  ten  years  later  he  announced  that  the  correct  ratio 
is  1  to  15.882  (38).  In  the  course  of  this  elaborate  research  on  the  com- 
bining volumes  and  compressibilities  of  gases,  made  with  a  view  to  calcu- 
lating their  molar  volumes  under  limiting  conditions,  Lord  Rayleigh  also 
measured  the  density  of  nitrogen  (40). 

Although  the  oxygen  which  he  prepared  by  three  different  methods 
all  had  the  same  density,  his  results  with  nitrogen  were  puzzling.  The 
nitrogen  he  prepared  from  ammonia  was  always  lighter  by  about  five  parts 
in  one  thousand  than  that  which  he  prepared  by  absorbing  the  oxygen, 
carbon  dioxide,  and  moisture  from  the  atmospheric  air.  He  then  wrote  to 
the  English  magazine,  Nature,  asking  the  readers  to  submit  explanations, 
but  none  were  received  ( 39 ) . 

Lord  Rayleigh  himself  thought  of  four  possible  explanations:  (1) 
the  nitrogen  he  had  prepared  from  the  atmosphere  might  still  contain 
some  oxygen;  (2)  the  nitrogen  prepared  from  ammonia  might  be  slightly 
contaminated  with  hydrogen;  (3)  the  nitrogen  from  the  atmosphere 
might  contain  some  N3  molecules  analogous  to  ozone;  or  (4)  some  of  the 
molecules  in  the  nitrogen  from  ammonia  might  have  decomposed  and  thus 
decreased  the  density  of  the  gas  (40,  45). 

The  first  hypothesis  was  most  improbable,  for,  because  of  the  very 
slight  difference  in  the  densities  of  oxygen  and  nitrogen,  the  contamina- 
tion would  have  had  to  be  very  great  in  order  to  account  for  the  dis- 
crepancy of  five  parts  in  one  thousand.  Lord  Rayleigh  showed  experi- 
mentally that  the  nitrogen  prepared  from  ammonia  was  entirely  free  from 
hydrogen.  The  third  hypothesis  was  not  encouraging  for  he  was  unable 
to  increase  the  density  of  his  nitrogen  by  passing  a  silent  discharge  through 
it.  It  was  then  that  Sir  William  Ramsay  obtained  permission  to  experiment 
with  the  atmospheric  nitrogen  (4,40). 

Since  these  experiments  led  to  such  surprising  and  important  results, 
it  may  be  well  to  devote  a  little  time  to  the  character  and  personality 
of  the  man  who  conceived  them.  William  Ramsay's  parents  were  both 
about  forty  years  old  when  they  married.  When,  in  the  following  year 
(October  2,  1852),  a  son  was  born  to  them,  the  happiness  of  these  good 
Scotch  parents  was  complete.  The  child  was  fond  of  nature,  music,  and 
books,  and  soon  developed  a  passion  for  learning  new  languages.  Friends 
of  the  family  often  wondered  how  the  active  little  fellow  could  sit  so 
quietly  through  the  long  Calvinist  sermons  at  Free  St.  Matthew's  Church 
in  Glasgow.  Whenever  they  looked  at  him  he  was  intently  reading  his 
Bible;  but,  if  they  had  been  close  enough,  they  would  have  seen  that  it 
was  never  an  English  Bible,  but  always  a  French  or  German  one.  The 
English  text  was  so  familiar  to  him  that  he  rarely  needed  to  consult  it, 


782 


DISCOVERY  OF  THE  ELEMENTS 


and  in  this  way  he  gained  his  first  knowledge  of  these  foreign  languages 
(5).  He  also  worked  out  many  of  his  propositions  in  geometry  from  the 
mosaics  in  the  church  windows  (6). 

Mr.  H.  B.  Fyfe,  one  of  his  classmates  at  the  Glasgow  Academy,  gave 
the  following  account  of  Ramsay's  first  chemical  experiments: 

At  that  time  he  knew  nothing  of  chemistry  theoretically,  but  he  had  for 
some  time  been  working  at  home  at  various  experiments  as  we  called  them. 
He  worked  in  his  bedroom,  and  there  were  a  great  many  bottles  always  about, 
containing  acids,  salts,  mercury,  and  so  on.  When  we  began  to  meet  in  this 
way,  I  found  he  was  quite  familiar  with  all  the  ways  of  getting  the  material  and 
apparatus  for  working  in  chemistry.  We  used  to  meet  at  my  house  in  the 
afternoons  and  do  what  practical  work  we  could,  making  oxygen  and  hydrogen 
and  various  simple  compounds,  such  as  oxalic  acid  from  sugar.  We  also  worked 
a  great  deal  with  glass.  .  .  .  We  used  to  work  with  mouth  blowpipes  and 
Bunsen  gas  burners  which  we  made  ourselves,  and  in  this  way  he  became 
exceedingly  expert  in  working  with  glass.  I  think  he  found  this  practice  very 
useful  in  after  life.  We  made  nearly  all  the  apparatus  we  used  except  flasks, 
retorts,  and  beakers.  .  .  .(6). 


Rudolf  Fittig,  1835-1910.  Professor  of 
organic  chemistry  at  Tubingen  and  Stras- 
bourg. He  discovered  the  lactones,  and 
devised  a  general  method  for  synthesiz- 
ing homologs  of  benzene.  With  Erdmann 
he  established  the  constitution  of  phenan- 
threne,  and  with  Remsen  he  proved  the 
constitution  of  the  alkaloid,  piperine. 
Sir  William  Ramsay  was  one  of  his 
students. 


William  Ramsay  always  excelled  in  wholesome  amusements  such 
as  walking,  cycling,  rowing,  swimming,  diving,  skating,  singing,  whistling, 
and  story-telling,  and  hence  had  a  host  of  friends.  Mr.  Fyfe  also  gave  a 
fine  description  of  Sir  William's  graceful  swimming  and  diving.  "When 


THE  INERT  GASES 


783 


we  were  in  Paris  in  1876,"  said  he,  "the  four  of  us  used  to  go  to  one  of 
the  baths  in  the  Seine  every  forenoon  and,  after  the  first  time,  when 
Ramsay  was  ready  to  dive,  the  bathman  would  pass  round  the  word  that 
the  Englishman  was  going  to  dive  and  every  one  in  the  establishment, 
including  the  washerwoman  outside,  would  crowd  in  and  take  up  positions 
to  watch  him"  (6). 

Sir  William  Ramsay  studied  at  Heidelberg  under  Bunsen  and  also 
at  Tubingen  under  Fittig,  and  it  was  at  the  latter  place  that  he  met  his 
life-long  American  friend,  Ira  Remsen  (49).  Although  Ramsay  later 
acquired  perfect  command  of  the  German  language,  his  first  words  to 


Ira  Remsen,  1846-1927.  Dis- 
tinguislied  American  chemist 
and  professor  of  organic  chemis- 
try. President  of  The  Johns 
Hopkins  University.  Author  of 
excellent  textbooks.  Founder 
and  editor  of  the  American 
Chemical  Journal.  Friend  of 
Sir  William  Ramsay.  He  in- 
vestigated the  composition  of 
commercial  saccharin. 


Courtesy  Alumni  Office,    The  Johns  Hopkins  University 


Remsen  sounded  like  this:  "Konnen  Sie  sagen  too  ist  die  Vorlesungs- 
zimmerP"  Remsen  puzzled  over  this  for  a  while,  and  said  with  a  smile, 
"Oh,  I  guess  you  want  the  lecture  room."  In  later  years  both  Remsen  and 
Ramsay  loved  to  tell  this  incident,  and  the  former  always  cherished  the 
honor  of  having  been  the  first  "to  open  the  big  front  door"  for  Sir  William 
Ramsay  (7). 

After  studying  on  the  Continent,   Ramsay  taught  chemistry  and 
engaged  in  research  at  Glasgow  and  later  at  University  College,  Bristol, 


784  DISCOVERY  OF  THE  ELEMENTS 

where  at  the  early  age  of  twenty-eight  years  he  was  appointed  Principal 
of  the  College  (63).  In  his  researches  on  the  physical  properties  of 
gases  he  acquired  remarkable  skill  in  manipulating  them. 

ARGON 

After  Ramsay  had  gained  permission  from  Lord  Rayleigh  to  investi- 
gate the  atmospheric  nitrogen,  he  passed  it  over  red-hot  magnesium  to 
find  out  whether  or  not  it  would  be  completely  absorbed.  After  the 
gas  had  been  passed  back  and  forth  over  the  hot  magnesium,  only  forty 
cubic  centimeters  of  it  remained,  and  this  residual  gas  was  about  15/14 
as  heavy  as  the  original  "nitrogen."  Professor  Ramsay  had,  of  course, 
taken  precautions  to  exclude  dust,  water,  and  carbon  dioxide.  After 
prolonged  treatment,  everything  was  absorbed  except  Vso  of  the  original 
volume.  (It  will  be  recalled  that  Cavendish  had  obtained  a  residue 
amounting  to  Vi2o  of  the  original  volume  (2).) 

The  gas  finally  obtained  had  a  density  of  19.086,  and  Ramsay  and 
Rayleigh  still  believed  it  to  be  a  modification  of  nitrogen,  similar  to  ozone. 
However,  when  Ramsay  examined  its  spectrum,  he  saw  not  only  the  bands 
of  nitrogen  but  also  groups  of  red  and  green  lines  which  had  never  before 
been  observed  in  the  spectrum  of  any  gas.  Sir  William  Crookes  made  a 
very  thorough  study  of  the  spectrum  and  observed  nearly  two  hundred 
lines  (28}. 

Rayleigh  and  Ramsay  then  worked  together,  exchanging  letters 
nearly  every  day.  On  May  24,  1894,  the  latter  wrote,  "Has  it  occurred 
to  you  that  there  is  room  for  gaseous  elements  at  the  end  of  the  first 
column  of  the  periodic  table?"  On  August  7,  he  wrote  again,  "I  think  that 
joint  publication  would  be  the  best  course,  and  I  am  much  obliged  to 
you  for  suggesting  it,  for  I  feel  that  a  lucky  chance  has  made  me  able  to 
get  Q  in  quantity  (there  are  two  other  X's,  so  let  us  call  it  Q  or  Quid?  .  .  . " 
(8). 

When  the  British  Association  met  at  Oxford  in  the  same  month, 
Ramsay  and  Rayleigh  astonished  the  members  by  announcing  the  dis- 
covery of  the  first  inert  gas,  which,  at  the  suggestion  of  Mr.  H.  G.  Madan, 
the  chairman,  they  proposed  to  call  argon,  the  lazy  one  (9,  25,  30). 

Lord  Rayleigh  died  in  1919  (41 ) .  M.  W.  Travers  said  that  in  all  the 
contemporary  correspondence  of  Sir  William  Ramsay  and  Lord  Rayleigh 
which  still  exists,  "there  is  no  indication  ...  of  suspicion  or  sense  of  in- 
justice on  either  side"  (40).  Visiting  scientists  were  always  surprised 
at  the  simplicity  of  the  latter's  apparatus.  Although  the  essential  instru- 
ments were  designed  and  constructed  with  the  utmost  skill,  the  less  impor- 
tant parts  were  assembled  with  little  regard  for  appearance.  His  papers 


THE  INERT  GASES  785 

were  written  in  a  clear,  polished  style  with  the  mathematical  portions  in 
concise,  elegant  form.  His  five  volumes  of  collected  contributions  are 
prefixed  with  the  motto  he  himself  chose:  "The  works  of  the  Lord  are 
great,  sought  out  of  all  them  that  have  pleasure  therein"  (41,  42). 

Soon  after  Lord  Rayleigh  and  Sir  William  Ramsay  discovered  argon 
in  1894,  H.  F.  Newall  and  W.  N.  Hartley  independently  observed  some 
new  lines  in  old  photographs  of  the  low-pressure  spectrum  of  the  air 
(66,  67).  "After  their  announcement  at  the  Oxford  meeting  of  the 
British  Association,"  said  Newall,  "it  seemed  for  many  reasons  natural  to 
borrow  the  first  letter  of  Lord  Rayleigh's  and  Professor  Ramsay's  names 
to  give  to  the  unknown  lines,  and  in  the  measurements  of  the  photo- 
graphs which  showed  the  lines  well,  there  appears  an  "R"  against  seven- 
teen lines  out  of  sixty-one  measured,  the  remaining  lines  being  known 
to  belong  to  mercury,  hydrogen,  nitrogen,  and  nitrocarbons.  It  tran- 
spires now,  as  I  learnt  from  reading  the  abstract  of  the  paper  in  which 
Lord  Rayleigh  and  Professor  Ramsay  describe  their  consummate  re- 
searches on  argon,  that  the  symbol  "A"  should  have  been  used  instead  of 
"R"  to  designate  the  lines  on  my  photographs.  For  the  lines  are  Argon 
lines"  (66).  The  lines  which  Newall  observed  in  these  photographs  of 
the  spectrum  of  the  air  coincided  closely  in  wave  length  with  the  ones 
Sir  William  Crookes  had  measured  for  the  blue  and  red  spectra  of  argon 
(66).  The  photographs  in  which  W.  N.  Hartley  observed  the  lines  of 
argon  were  taken  in  1882  (67). 

Soon  after  hearing  of  the  discovery  of  argon,  Lecoq  de  Boisbaudran 
predicted  that  it  might  belong  to  a  family  of  absolutely  ineit  elements 
all  of  which  were  then  unknown,  and  that  their  atomic  weights*  would  be: 
20.0945,  36.40  ±  0.08,  84.01  ±  0.20,  and  132.71  ±  0.15.  He  also  pre- 
dicted that  the  first  two  of  these  elements  would  be  more  abundant  than 
the  others  (33,34). 

In  1907  Lord  Rayleigh  showed  that  many  rocks,  such  as  Matopo 
granite  and  syenite  from  Mt  Sorrel  in  Leicestershire  and  from  Norway, 
which  contain  helium  also  contain  argon  (68). 

Although  traces  of  argon  are  present  in  the  gases  of  the  blood,  it  does 
not  appear  to  play  any  direct  role  in  metabolism  (69).  Bacteria  in  the 
nodules  of  leguminous  plants  absorb  argon  with  the  nitrogen,  but  no 
fixation  of  the  argon  occurs  (69). 

HELIUM 

In  the  year  1868  the  French  astronomer  Pierre-Jules-Cesar  Janssen 
(43,  44)  went  to  India  to  observe  a  total  eclipse  of  the  sun  and  to  make 

*  The  1955  atomic  weights  of  the  noble  gases  are:     helium,  4.003;  neon,  20.183; 
argon,  39.944;  krypton,  83.80;  xenon,  131.30;  and  radon,  222. 


786 


DISCOVERY  OF  THE  ELEMENTS 


the  first  spectroscopic  study  of  its  chromosphere  (36).  He  noticed  a 
yellow  line,  D3,  which  did  not  quite  coincide  with  the  D-line  of  sodium, 
and  which  he  could  not  reproduce  in  the  laboratory.  When  the  English 
astronomer  Sir  Norman  Lockyer  (22)  found  that  the  new  line  did  not 
belong  to  hydrogen  or  to  any  element  then  known,  he  named  it  helium 
for  the  sun  (50),  and  for  a  quarter  of  a  century  helium  was  regarded  as 
a  hypothetical  element  which  might  possibly  exist  on  the  sun,  but  which 
had  never  been  found  on  the  earth  ( 10, 20,  35 ) .  In  some  of  his  researches 
leading  up  to  the  discovery  of  solar  helium,  Lockyer  was  assisted  by 
Professor  Edward  Frankland  (37).  Frankland  believed  however  that 


Pierre-Jules-Cesar  Janssen,*  1824-1907. 

French  astronomer  who  directed  many 
astronomical  expeditions.  Member  of 
the  French  Institute  and  of  the  Bureau 
of  Longitude.  In  1868  he  observed  in 
the  sun's  chromosphere  a  yellow  line, 
D3,  which  is  now  known  to  belong  to 
the  element  helium.  He  was  the  direc- 
tor of  the  astrophysical  observatory  at 
Meudon. 


From  Lebon's  "Histoire  Abregee  de 
rAstronomie" 


the  new  yellow  line  might  possibly  be  due  to  hydrogen  and  that  with 
an  extremely  long  tube  of  hydrogen  it  might  be  possible  to  detect  the 
line  (22).  For  more  than  a  quarter  of  a  century  most  spectroscopists 
doubted  the  existence  of  Lockyer's  "helium"  and  some  went  so  far  as  to 
ridicule  it  (22). 

John  W.  Draper,  first  president  of  the  American  Chemical  Society, 
however,  appreciated  the  full  import  of  Lockyer's  prediction,  and  on 
November  16,  1876,  declared  in  his  inspiring  presidential  address: 

"And  now,  while  we  have  accomplished  only  a  most  imperfect  ex- 

*  Reproduced  from  E.  LEBON'S  "Histoire  Abregee  de  rAstronomie"  by  permission  of 
Gauthier-Villars  et  Cie.,  55  Quai  des  Grands- Augustas,  Paris. 


THE  INERT  GASES  787 


French  Medallion*  Cast  in  1878  in  honor  of  the  French  astronomer,  Jules 
Janssen,  and  the  English  astronomer,  Sir  Norman  Lockyer,  for  their  method 
of  analyzing  the  solar  protuberances. 

animation  of  objects  that  we  find  on  the  earth,  see  how,  on  a  sudden, 
through  the  vista  that  has  been  opened  by  the  spectroscope,  what  a 
prospect  lies  beyond  us  in  the  heavens!  I  often  look  at  the  bright  yellow 
ray  emitted  from  the  chromosphere  of  the  sun,  by  that  unknown  element, 
Helium,  as  the  astronomers  have  ventured  to  call  it.  It  seems  trembling 
with  excitement  to  tell  its  story,  and  how  many  unseen  companions  it 
has.  And  if  this  be  the  case  with  the  sun,  what  shall  we  say  of  the 
magnificent  hosts  of  the  stars?  May  not  every  one  of  them  have  special 
elements  of  its  own?  Is  not  each  a  chemical  laboratory  in  itself?'7  (65). 

In  the  light  of  present  knowledge  however  the  name  helium  is  a 
misnomer,  for  it  has  the  suffix  -ium  which  is  characteristic  of  the  names 
of  the  metals. 

In  1881  L.  Palmieri  thought  he  detected  helium  in  a  yellow  amor- 
phous sublimation  product  from  Vesuvius.  When  he  heated  it  in  the 
Bunsen  flame,  he  was  able  to  observe  the  D3  spectroscopic  line  with  a 
wave  length  of  5875  Angstrom  units  (69,  70).  Although  R.  Nasini  and 
F.  Anderlini  were  unable  in  1906  to  produce  this  line  by  similarly  heating 
minerals  known  to  contain  helium,  they  believed  that,  if  the  helium  in 
Palmieri's  mineral  was  bound  endothermally,  he  might  possibly  have 
observed  its  spectrum  in  this  manner  ( 69,  71 ) . 

In  1888—90  the  great  American  mineralogical  chemist  William  F. 
Hillebrand  (46)  noticed  that,  when  the  mineral  uraninite  is  treated  with 
a  mineral  acid,  an  inert  gas  is  evolved,  which  he  believed  to  be  nitrogen. 

*  Reproduced  from  LOCKYER,  T.  MARY,  AND  WINIFRED  L.  LOCKYER,  "The  Life  and 
Work  of  Sir  Norman  Lockyer,"  hy  permission  of  Macmillan  and  Co. 


788 


DISCOVERY  OF  THE  ELEMENTS 


Sir  Joseph  Norman  Lockyer,*  1836- 
1920.  Director  of  the  solar  physics  ob- 
servatory of  The  Royal  College  of  Sci- 
ence at  South  Kensington.  Pioneer  in 
the  spectroscopy  of  the  sun  and  stars. 
In  1868  Lockyer  and  Janssen  independ- 
ently discovered  a  spectroscopic 
method  of  observing  the  solar  promi- 
nences in  daylight.  Such  observa- 
tions had  previously  been  made  only 
at  the  time  of  total  eclipses  of  the  sun. 


When  Sir  William  Ramsay  read  the  paper,  he  disagreed  with  this  ex- 
planation, and  repeated  the  experiment,  using,  however,  a  related  uranium 
mineral  called  cleveite  (11,  61).  He  obtained  a  little  nitrogen,  as  Hille- 
brand  had  done,  but  also  argon  and  another  gas  with  different  spectral 
lines.  Since  Ramsay  did  not  have  a  very  good  spectroscope,  he  sent 
some  specimens  of  the  unknown  gas  to  Sir  Norman  Lockyer  and  to  Sir 
William  Crookes  for  examination.  Lockyer  said,  "When  I  received  it 
from  him,  the  glorious  yellow  effulgence  of  the  capillary,  while  the  current 
was  passing,  was  a  sight  to  see"  (27). 

On  March  17,  1895,  Ramsay  wrote  to  Mr.  J.  Y.  Buchanan,  "Crookes 
thinks  its  spectrum  is  new,  and  I  don't  see  from  the  method  of  treatment 
how  it  can  be  anything  old,  except  argon,  and  that  it  certainly  is  not.  We 
are  making  more  of  it,  and  in  a  few  days  I  hope  we  shall  have  collected 
enough  to  do  a  density.  I  suppose  it  is  the  sought-for  krypton,  an 
element  which  should  accompany  argon.  .  .  ."  Before  a  week  had  passed, 
the  new  gas  was  shown  to  be  identical  with  Lockyer's  solar  element, 
helium  (21,23,24,  26,52). 

On  March  24  Sir  William  wrote  to  Lady  Ramsay: 

Let's  take  the  biggest  piece  of  news  first.  I  bottled  the  new  gas  in  a 
vacuum  tube,  and  arranged  so  that  I  could  see  its  spectrum  and  that  of  argon 

*  Reproduced  from  LOCKYER,  T.  MARY,  and  WINIFRED  L.  LOCKYER,  "The  Life  and 
Work  of  Sir  Norman  Lockyer,"  by  permission  of  Macmillan  and  Co. 


THE   INERT   GASES  789 

in  the  same  spectroscope  at  the  same  time.  There  is  argon  in  the  gas;  but 
there  was  a  magnificent  yellow  line,  brilliantly  bright,  not  coincident  with,  but 
very  close  to,  the  sodium  yellow  line.  I  was  puzzled,  but  began  to  smell  a  rat. 
I  told  Crookes,  and  on  Saturday  morning  when  Harley,  Shields,  and  I  were 
looking  at  the  spectrum  in  the  dark-room,  a  telegram  came  from  Crookes.  He 
had  sent  a  copy  here  and  I  enclose  that  copy.  You  may  wonder  what  it  means. 
Helium  is  the  name  given  to  a  line  in  the  solar  spectrum,  known  to  belong 
to  an  element,  but  that  element  has  hitherto  been  unknown  on  the  earth.  Kryp- 
ton was  what  I  called  the  gas  I  gave  Crookes,  knowing  the  spectrum  to  point 
to  something  new.  587.49  is  the  wave-length  of  the  brilliant  line.  It  is  quite 
overwhelming  and  beats  argon.  I  telegraphed  to  Berthelot  at  once  yesterday: 
Gas  obtained  by  me  deveite  mixture  argon  helium.  Crookes  identifies  spec- 
trum. Communicate  Academy  Monday  .  .  .  Ramsay9'  (12,  29). 

C.  Runge  and  Paschen  found,  however,  that  the  spectrum  of  the 
gas  from  cleveite  gave  a  yellow  line  which  was  double.  Not  until  the 
D3  line  of  solar  helium  had  also  been  conclusively  proved  to  be  double, 
did  Runge  and  Paschen  admit  the  existence  of  helium  in  cleveite  (69,  72). 

In  1895  H.  Kayser  discovered  the  presence  of  helium  in  the  atmos- 
phere of  Bonn,  Germany  (73).  This  observation  was  soon  confirmed  by 
Siegfried  Friedlander,  who  detected  minute  amounts  of  it  spectro- 
scopically  in  the  atmosphere  of  Berlin,  and  also  by  E.  C.  C.  Baly,  who  in 
1898  demonstrated  spectroscopically  the  existence  of  helium  in  crude 
neon,  thus  indirectly  proving  it  to  be  a  constituent  of  the  atmosphere 
(74,75). 

When  W.  F.  Hillebrand  discovered  the  presence  of  nitrogen  in 
uraninite  he  considered  it  well  worthy  of  further  study  but  because  of 
urgent  official  duties  was  unable  to  investigate  it  thoroughly.  In  one 
of  his  letters  to  Sir  William  Ramsay  he  wrote:  "It  doubtless  has  ap- 
peared incomprehensible  to  you  in  view  of  the  bright  argon  and  other 
lines  noticed  by  you  in  the  gas  from  cleveite  that  they  should  have 
escaped  my  observation.  They  did  not."  As  Edgar  Fahs  Smith  once 
stated,  "The  modesty  and  nobility  of  Hillebrand  shine  forth  in  his  beauti- 
ful letters  to  Ramsay"  (64). 

In  the  meantime  Per  Theodor  Cleve,  the  Swedish  chemist  for  whom 
the  mineral  cleveite  had  been  named  by  its  discoverer,  A,  E.  Nordenskiold, 
had  his  student  Nils  Abraham  Langlet  investigate  it  (53).  Although 
Ramsay  announced  the  discovery  before  Cleve  and  Langlet  had  com- 
pleted their  research,  the  Swedish  chemists  were  independent  dis- 
coverers of  helium.  Langlet's  first  helium  was  purer,  in  fact,  than  Ram- 
say's, for  he  obtained  a  much  better  value  for  its  atomic  weight  (13,  31, 
32).  The  spectroscopic  measurements  were  made  by  Professor  Robeit 
Thalen  (47). 

Sir  Norman  Lockyer's  "Story  of  helium,"  published  in  Nature  on 


790 


DISCOVERY  OF  THE  ELEMENTS 


February  6  and  13,  1896  and  reprinted  with  additions  in  the  biography 
by  T.  Mary  Lockyer  and  Winifred  L.  Lockyer,  is  a  masterpiece  of  clear, 
understandable  scientific  literature  (22).  In  1899  Sir  Norman  Lockyer 
detected  helium  in  the  water  of  the  Harrogate  springs  (22). 

Immediately  after  the  discovery  of  argon  and  helium,  Professor 
Raffaello  Nasini  of  Padua  and  his  collaborators  began  to  search  for  them 
in  the  natural  products  of  Italy,  especially  in  the  gaseous  emanations. 
Traveling  hour  after  hour  by  carriage,  on  horseback,  by  mule,  or  on  foot, 
using  portable  improvised  apparatus  in  the  field,  they  devoted  many  years 
to  careful  analyses  of  the  natural  gases  of  Italy  (54,  85).  In  1898  they 
detected  helium  in  the  volcanic  gases  from  Monte  Irone  and  in  the  boric 
acid  soffioni  in  Tuscany  (55).,  It  was  found  only  in  minute  amounts,  and 
in  1897  Clemens  Winkler  ranked  it  "among  the  rarest  of  elements"  (56). 


Per  Teodor  Cleve,  1840-1905.  Pro- 
fessor of  chemistry  at  Upsala.  Chair- 
man of  the  Nobel  Committee  for  chem- 
istry. Cleve  and  Nils  Abraham  Langlet 
were  independent  discoverers  of  terres- 
trial helium.  Sir  William  Ramsay's  an- 
nouncement was  made  before  their  re- 
search was  completed. 


A  few  years  later  an  abundant  source  of  helium  was  found  in  natural 
gas.  In  1903  a  gas  well  was  started  near  the  town  of  Dexter,  Kansas.  In 
honor  of  the  new  well  a  dedication  ceremony  was  planned  at  which  a 
portion  of  the  gas  drawn  off  through  a  small  pipe  was  to  be  lighted  in 
presence  of  a  large  group  of  citizens  and  invited  guests.  At  the 
appointed  time  they  looked  forward  expectantly  to  the  sight  of  a  large  jet 
of  flame  which  would  usher  in  prosperity  for  the  little  town  of  Dexter, 
but  to  their  astonishment  the  torch  that  was  supposed  to  light  the  gas 
was  extinguished  (62).  An  early  account  of  this  historic  occasion  reads: 


THE  INERT  GASES 


791 


"It  was  soon  closed  in,  and  an  attempt  was  made  to  burn  it,  as  natural 
gas  is  usually  burned,  for  generating  steam  for  drilling  purposes.  Much 
to  the  surprise  of  parties  interested,  it  would  not  bum.  Later  it  was 
found  that  when  a  fire  was  already  kindled  in  a  fire  box  or  an  engine  and 
the  gas  turned  on,  .  .  .  it  would  begin  to  burn  and  would  develop  suffi- 
cient heat  to  generate  steam  moderately  well.  But  as  soon  as  the  coal  or 
other  fuel  in  the  firebox  was  consumed,  the  gas  would  no  longer  burn. 
A  cylinder  of  the  gas  was  shipped  to  the  University  of  Kansas  later 
during  the  summer  and  was  partially  examined  by  members  of  the  chemi- 
cal and  geological  departments.  .  .  .  The  owners  of  the  well  .  .  .  did  not 
wish  it  given  great  publicity"  (57). 


Hamilton  P.  Cady,  1874-1943.  Codis- 
coverer  with  D.  F.  McFarland  of  the 
presence  of  helium  in  the  natural  gases  of 
Kansas;  pioneer  in  research  with  liquid 
ammonia.  A  few  years  before  the  close 
of  his  life,  Dr.  Cady  perfected  an  instru- 
ment for  determining  molecular  weights 
rapidly  and  precisely.  See  ref.  (60). 


Courtesy  Robert  Toft 


The  strange  gas  was  investigated  by  E.  Haworth  and  D.  F.  Mc- 
Farland of  the  University  of  Kansas  (57,  58).  McFarland's  analysis  of 
it  showed  the  presence  of  about  15  per  cent  methane,  72  per  cent  nitro- 
gen, 12  per  cent  inert  residue,  and  small  amounts  of  oxygen  and  hydrogen. 
In  an  analysis  of  natural  gas  it  had  been  customary  to  report  the  nitrogen 
by  difference,  i.e.,  to  determine  the  percentages  of  the  other  constituents 
separately  and  subtract  the  total  from  100  per  cent,  reporting  the  dif- 
ference as  nitrogen.  Because  of  the  abnormally  high  inert  residue  from 
this  gas,  however,  McFarland  had  determined  the  nitrogen  directly 
and  yet  had  found  an  appreciable  residue  that  could  not  be  gotten  rid 


792  DISCOVERY  OF  THE  ELEMENTS 

of  chemically.  Thinking  that  this  inert  residue  might  contain  argon 
or  some  other  member  of  the  group  of  recently  discovered  gases,  Dr. 
H.  P.  Cady  and  McFarland  investigated  it  further  (59)  and  found  that 
it  contained  1.84  per  cent  of  helium  (84). 

With  the  aid  of  cocoanut  charcoal  chilled  to  the  temperature  of 
liquid  air  they  were  able  to  absorb  the  constituents  other  than  helium 
and  obtain  the  latter  rather  easily,  especially  after  the  University  of 
Kansas  purchased  a  small  liquid  air  plant  for  that  purpose.  On  examin- 
ing many  other  natural  gases  from  fields  in  Kansas  and  elsewhere  they 
found  helium  in  almost  every  specimen  (59).  The  price  of  helium  then 
fell  from  $2500  per  cubic  foot  in  1915  to  3  cents  a  cubic  foot  in  1926  (62). 
Since  helium  is  a  light  gas  like  hydrogen  yet  does  not  burn  nor  form 
explosive  mixtures  with  air,  it  is  used  for  inflating  balloons  and  dirigibles, 
thus  adding  enormously  to  the  safety  of  such  ascensions  and  flights. 

Using  apparatus  similar  to  that  of  Cady  and  McFarland,  Emerich 
Czako  of  Karlsruhe  in  1913  detected  helium  in  the  natural  gas  from 
several  Austrian,  Hungarian,  German,  and  Alsatian  wells  and  measured 
the  radioactivity  of  the  gases.  He  also  found  helium  in  the  gases  from 
hot  springs  of  the  Wildbad  health  resort  in  the  Black  Forest,  thus  con- 
firming H.  Kayser's  results  of  1895  (73,  76). 

KRYPTON 

Since  the  atomic  weights  of  argon  and  helium  were  found  to  be 
about  40  and  4,  respectively,  Ramsay  thought  that  these  gases  might 
possibly  belong  to  a  new  group  of  the  periodic  system  and  that  there 
must  be  an  intermediate  member  with  an  atomic  weight  of  approxi- 
mately :< 20  (63).  In  this  search  he  was  aided  by  his  assistant  Morris 
William  Travqrs. 

I>r.  Travers,  who  was  born  in  London  on  January  24,  1872,  studied  at 
University  College,  and  received  his  doctorate  in  1893.  Soon  after 
this  he  became  intensely  interested  in  Sir  William  Ramsay's  remarkable 
new  elements  and  in  the  possibility  of  discovering  another  one  between 
helium  and  argon  and  two  others  of  higher  atomic  weight  than  argon. 

Ramsay  and  Travers  tried  in  vain  to  find  these  new  gases  by  heating 
rare  minerals.  Their  next  attempt,  and,  in  fact,  their  only  hope,  was  to 
diffuse  argon  to  separate  it,  if  possible,  into  two  fractions  of  different 
density.  Dr.  William  Hampson  presented  them  with  about  a  liter  of 
liquid  air,  which  they  used,  not  for  liquefying  the  argon,  but  for  obtaining 
sufficient  skill  in  manipulation  so  that  they  would  not  risk  losing  their 
precious  fifteen  liters  of  argon.  They  were  careful,  moreover,  to  save  the 
residues  of  the  liquid  air  in  the  hope  that  these  might  contain  some  higher- 
boiling  constituents.  The  residue  left  after  most  of  the  liquid  air  had 


THE  INERT   GASES 


793 


boiled  away  consisted  largely  of  oxygen  and  nitrogen,  which  Ramsay  and 
Travers  removed  with  red-hot  copper  and  magnesium  (18,  19). 

One  day  as  the  younger  chemist  returned  to  the  laboratory  after 
lunch,  a  colleague  called  gaily  to  him,  "It  will  be  the  new  gas  this  time, 
Travers,"  and  with  pretended  self-confidence  he  replied,  "Of  course  it 
will  be."  Ramsay  and  Travers  then  examined  the  twenty-five  cubic 
centimeters  of  residual  gas,  and  when  they  found  it  to  be  inert,  they  im- 
mediately placed  it  in  a  Plucker  tube  connected  to  an  induction  coil 
and  observed  its  spectrum.  There  was  a  bright  yellow  line  with  a  greener 
tint  than  that  of  the  helium  line  and  a  brilliant  green  line  that  did  not 
coincide  with  any  line  of  argon,  helium,  mercury,  or  hydrogen  (14). 


Sir  William  Ramsay,  1852- 
1916.  Scottish  chemist  and 
physicist  who,  with  Lord  Ray- 
leigh  and  M.  W.  Travers,  dis- 
covered the  inert  gases: 
helium,  neon,  argon,  krypton, 
and  xenon.  He  also  made  a 
remarkable  determination  of 
the  atomic  weight  of  radon 
(radium  emanation),  the  heav- 
iest of  the  inert  gases. 


They  discovered  this  gas  on  May  30,  1898,  and  named  it  krypton, 
meaning  hidden  (15).  After  working  until  eleven  o'clock  that  evening 
on  a  density  determination  of  the  new  gas,  Ramsay  and  Travers  found 
that  it  belonged  between  bromine  and  rubidium  in  the  periodic  table, 
and  so  great  was  their  excitement  that  the  younger  chemist  almost  forgot 
about  his  examination  for  doctor  of  science  which  had  been  scheduled  for 
the  next  day  (14). 


794  DISCOVERY  OF  THE  ELEMENTS 

NEON 

Although  krypton  was  undoubtedly  a  new  element  of  the  zero  group, 
it  was  not  the  one  for  which  they  had  been  looking.  The  gas  they  had 
been  expecting  to  find  would  have  appeared  in  the  more  volatile  portion 
of  the  argon.  Continuing  their  search  for  this  lighter  gas,  Professor 
Ramsay  and  Dr.  Travers  liquefied  and  solidified  the  argon  by  surround- 
ing three  liters  of  it  with  liquid  air  boiling  under  reduced  pressure, 
allowed  the  argon  to  volatilize,  and  collected  the  portion  that  distilled 
off  first.  This  had  a  complex  spectrum  which  Ramsay  described  in  his 


Morris  William  Travers.  Honorary 
professor  at  the  University  of  Bristol. 
Formerly  director  of  the  Indian  Institute 
of  Science  in  Bangalore  Co-discoverer 
with  Sir  William  Ramsay  of  the  inert 
gases,  neon,  krypton,  and  xenon.  He  is 
an  authority  on  glass  technology. 


notes  as  follows:  "Lightest  fraction  of  all.  This  gave  magnificent  spec- 
trum with  many  lines  in  red,  a  number  of  faint  green,  and  some  in  violet. 
The  yellow  line  is  fairly  bright,  and  persists  at  very  high  vacuum,  even 
phosphorescence"  (16). 

The  vacuum  tube  containing  this  most  volatile  fraction  of  the  argon 
immediately  convinced  them  that  it  must  be  a  new  gas,  for,  said  Dr. 
Travers: 

The  blaze  of  crimson  light  from  the  tube  told  its  own  story,  and  it  was  a 
sight  to  dwell  upon  and  never  to  forget.  It  was  worth  the  struggle  of  the  pre- 


THE  INERT  GASES  795 

vious  two  years;  and  all  the  difficulties  yet  to  be  overcome  before  the  research 
was  finished.  The  undiscovered  gas  had  come  to  light  in  a  manner  which  was 
no  less  than  dramatic.  For  the  moment,  the  actual  spectrum  of  the  gas  did  not 
matter  in  the  least,  for  nothing  in  the  world  gave  a  glow  such  as  we  had  seen 
(16). 

Willie  Ramsay,  Sir  William's  thirteen-year-old  son,  inquired,  "What 
are  you  going  to  call  the  new  gas?  I  should  like  to  call  it  novum."  His 
father  liked  the  suggestion,  but  thought  that  the  synonymous  term,  neon, 
would  sound  better,  and  it  is  by  this  name  that  the  gas  discovered  in 
June,  1898,  is  now  known  (16).  In  the  brilliant  neon  signs  on  every  busi- 
ness street  one  may  now  see  at  night  the  "blaze  of  crimson  light"  that 
brought  such  deep  satisfaction  and  contentment  to  Professor  Ramsay  and 
Dr.  Travers. 

Since  Ramsay  and  Travers  discovered  neon  in  the  most  volatile  por- 
tion of  their  argon  (69),  this  immediately  established  the  occurrence  of 
neon  in  the  atmosphere.  In  1909  Armand  Gautier  showed  that  the 
fumaroles  of  Vesuvius  and  the  gas  which  bubbled  from  the  hot  springs 
in  an  old  crater  at  Agnano,  near  Naples,  contained  neon  ( 69,  77 ) . 

XENON 

With  the  aid  of  a  new  liquid-air  machine,  generously  provided  by 
Dr.  Ludwig  Mond,  Professor  Ramsay  and  Dr.  Travers  prepared  larger 
quantities  of  krypton  and  neon,  and  by  repeated  fractionation  of  krypton, 
a  still  heavier  gas  was  separated  from  it,  which  they  named  xenon,  the 
stranger  (15).  It  was  discovered  on  July  12,  1898.  Vacuum  tubes  con- 
taining it  show  forth  a  beautiful  blue  glow. 

Sir  William  Ramsay  (48)  had  a  rare  sense  of  humor.  He  once  said 
of  his  visit  to  the  Norwegian  chemist,  Peter  Waage,  "He  speaks  a  little 
German,  and  with  my  knowledge  of  Norse,  which  as  you  know  is  surpassed 
by  few  and  equalled  by  none  of  the  natives  of  that  country,  we  got  on 
very  well."  In  writing  of  a  certain  pleasure  trip,  he  said,  "I  went  to 
Paris  with  three  spirits  more  wicked  than  myself,  lawyers  ...  a  fearful 
compound,  3  lawyers  and  a  chemist  .  .  .  just  like  NC13  for  all  the  world, 
liable  to  explode  at  any  moment"  (17). 

Sir  William  was  also  one  of  the  finest  linguists  the  scientific  world 
ever  produced.  He  could  lecture  in  perfect  German  before  a  cultured 
German  audience,  or  in  French  before  an  assembly  of  French  scientists. 
When  presiding  in  1913  over  the  International  Association  of  Chemical 
Societies,  he  astonished  and  delighted  his  cosmopolitan  audience  by  speak- 
ing first  in  English,  then  in  French,  then  in  German,  and  occasionally  in 
Italian,  always  with  perfect  grace  and  composure.  In  spite  of  his  splendid 
command  of  languages,  his  sense  of  humor  sometimes  led  him  to  write 


796  DISCOVERY  OF  THE  ELEMENTS 

to  members  of  his  family  in  the  following  vein:  "Mi  Car  Dora,  .  .  .  lo 
hab  recip  vestr  litr,  ke  era  mult  facil  a  comprendar  .  .  ."  (17). 

Ramsay's  extended  travels  never  dulled  the  enthusiasm  with  which  he 
visited  new  scenes.  Americans  may  read  with  pleasure  his  description 
of  Great  Falls,  Montana: 

It  is  a  pretty  town  and  perfectly  civilized.  By  the  way,  in  all  American 
towns  the  electric  car  is  the  chief  feature.  There  are  overhead  wires,  and  cars 
like  our  tram  cars  run  at  a  prodigious  rate,  careless  of  life  apparently,  yet  there 
are  very  few  accidents.  I  suppose  the  fittest,  i.e.,  those  who  don't  get  killed, 
survive.  They  are  delightful  as  a  form  of  motion  and  almost  rival  the  bicycle. 
That  creature,  too,  has  penetrated  everywhere,  and  is  used  even  over  the 
prairie  (17). 

Sir  William  Ramsay's  later  work  on  radioactivity  is  regarded  as  even 
more  remarkable  than  his  discovery  of  the  inert  gases.  He  died  on  July 
23,  1916,  about  three  years  before  the  death  of  his  distinguished  collabora- 
tor, Lord  Rayleigh. 

Dr.  Travers  served  from  1906  to  1914  as  director  of  the  Indian  In- 
stitute of  Science  in  Bangalore,  and  in  1921  he  became  president  of  the 
Society  of  Glass  Technology  (51).  He  is  an  honorary  professor  at  the 
University  of  Bristol.  In  1928  he  wrote  a  book  entitled  "The  Discovery 
of  the  Rare  Gases,"  which  is  illustrated  with  pictures  of  apparatus  and 
facsimile  pages  from  Sir  William  Ramsay's  notebooks  ( 9 ) . 

In  1920  Charles  Moureu  and  A.  Lepape  detected  all  of  the  noble  gases 
in  the  natural  gas  of  Alsace-Lorraine  (69,  78).  Moureu  also  found 
krypton  and  xenon  in  many  French  spring  waters  such  as  those  of  Aix-les- 
Bains,  Audinac,  Bagneres-de-Bigorre,  Bagneres-de-Luchon,  Balaruc,  and 
Vichy  (69,  79). 

Charles  Moureu  was  born  on  April  19,  1863,  in  the  little  village  of 
Mourenx  near  Pau  in  southern  France.  In  early  infancy  he  had  the 
great  misfortune  to  lose  his  father.  Since  Charles  was  the  youngest  of 
seven  children  in  a  humble  peasant  home,  his  widowed  mother  had  a 
great  struggle  to  give  him  the  education  which  his  rapidly  developing 
talents  deserved.  His  affectionate  brother  Felix,  who  had  become  a 
successful  pharmacist  at  Biarritz,  helped  and  encouraged  him  in  his 
secondary  studies,  however,  and  gave  him  practical  instruction  in  phar- 
macy. 

In  his  studies  at  the  Ecole  Superieure  de  Pharmacie  in  Paris,  Charles 
Moureu  made  an  outstanding  record.  In  1907  he  became  professor  of 
pharmaceutical  chemistry,  and  ten  years  later  he  accepted  the  chair  of 
organic  chemistry  at  the  College  de  France  as  M.  Berthelot's  successor. 

Although  most  of  his  work  was  done  in  the  fields  of  organic  and 
theoretical  chemistry,  Moureu  and  his  assistants  also  devoted  much 


THE  INERT  GASES  797 

thought  to  the  rare  gases  of  the  atmosphere  and  their  geological  signifi- 
cance. In  1895  he  detected  argon  and  helium  in  a  natural  source  of 
nitrogen  (80).  He  investigated  many  subterranean  gases  from  wells 
and  mines  and  showed  that  they  contain  helium,  neon,  argon,  krypton, 
xenon,  and  radon  and  its  isotopes. 

Since  the  rare  gases  are  inert,  they  could  not  be  detected  by  means 
of  any  chemical  reaction.  Since  they  were  too  highly  diluted  in  the 
natural  gases,  it  was  impossible  to  detect  the  inert  gases  by  direct  spectro- 
scopic  examination.  Preliminary  removal  of  carbon  dioxide,  oxygen,  and 
nitrogen  by  chemical  means  was  therefore  necessary.  After  measuring 
the  total  volume  of  the  rare  gases  at  a  known  temperature  and  pressure, 
Moureu  and  his  collaborators  subjected  the  mixture  to  fractionation,  using 
cocoanut  charcoal  chilled  with  liquid  air.  As  Sir  James  Dewar  had  shown, 
the  charcoal  absorbed  the  most  easily  condensable  and  heavier  gases, 
xenon,  krypton,  and  argon,  while  the  lighter  gases,  neon  and  helium, 
remained  free.  After  drawing  off  the  light  gases  by  suction,  Moureu 
heated  the  cocoanut  charcoal  to  disengage  the  heavy  gases,  thus  separat- 
ing the  rare  gases  into  two  groups,  which  could  be  further  fractionated. 

In  1911  Moureu  and  Lepape  found  that,  although  the  neon,  argon, 
krypton,  and  xenon  in  natural  gases  are  always  present  in  a  fixed  pro- 
portion, the  proportion  of  helium  to  the  other  gases  (since  helium 
is  continually  being  created  by  disintegration  of  radioactive  elements) 
varies  within  wide  limits. 

Since  nitrogen,  a  "relatively  inert"  element,  "always  accompanies 
the  rare  gases,  of  which  it  is  the  constant  diluant,"  it  is  easy  to  tell 
whether  a  given  specimen  of  nitrogen  is  of  mineral  origin  or  the  result 
of  the  decomposition  of  nitrogen  compounds  or  of  nitrogenous  organic 
matter.  According  to  Moureu,  the  nitrogen  in  fire  damp  is  of  mineral 
origin  and  always  contains  the  rare  gases. 

Moureu  and  his  collaborators,  unfortunately,  were  never  able  to 
find  any  source  of  neon,  argon,  krypton,  and  xenon  that  would  be  easier 
to  exploit  than  the  atmosphere.  M.  Georges  Claude  however  succeeded 
in  tapping  this  difficult  but  limitless  source  of  the  rare  gases  and  developed 
from  it  a  wonderful  new  field  of  illumination  (81,  S3). 

Charles  Moureu  was  editor  of  the  Annales  de  chimie  et  de  physique 
and  of  the  Revue  scientifique.  In  spite  of  his  many  scientific  honors  and 
duties,  he  always  maintained  affectionate  and  sympathetic  contacts  with 
the  humble  workers  with  whom  his  childhood  years  had  been  spent.  He 
died  at  Biarritz  on  June  13,  1929  (82). 

LITERATURE  CITED 

( 1 )     "Report  of  the  British  Association  for  the  Advancement  of  Science,"  41,  xci 
(1871).     Quotation  from  Lord  Kelvin. 


798  DISCOVERY  OF  THE  ELEMENTS 

(2)  RAMSAY  W.,  "The  Gases  of  the  Atmosphere.    The  History  of  Their  Discovery," 

Macmillan  and  Co.,  London,  1915,  p.  144;  T.  E.  THORPE,  "Scientific  Papers 
of  the  Honourable  Henry  Cavendish,"  Vol.  2,  Cambridge  University  Press, 
Cambridge,  England,  1921,  p.  193. 

(3)  "History  of  the  Cavendish  Laboratory,  1871-1910,"  Longmans,  Green  and  Co. 

London,  1910,  pp.  40-74.  Chapter  on  Lord  Rayleigh's  Professorship  by 
Glazebrook. 

(4)  RAMSAY,  W.,  "The  Gases  of  the  Atmosphere,"  Ref.  (2),  p.  158. 

(5)  TILDEN,  W.  A.,  "Sir  William  Ramsay,  Memorials  of  His  Life  and  Work,"  Mac- 

millan and  Co.,  London,  1918,  p.  12. 

(6)  Ibid.,  pp.  20-5. 

(7)  Ibid.,  p.  39. 

(8)  Ibid.,  p.  131. 

(9)  TRAVERS,  M.  W.,  "The  Discovery  of  the  Rare  Gases,"  Edward  Arnold  and  Co., 

London,  1928,  p.  22. 

(JO)  VON  MEYER,  ERNST,  "History  of  Chemistry,"  3rd  English  ed.  from  3rd  German, 
Macmillan  and  Co.,  London,  1906,  p.  245. 

(11)  CHAMBERLIN,  R.  T.,  "The  Gases  in  Rocks."   Carnegie  Inst,  Washington,  D.  C., 

1908,  p.  8. 

(12)  TILDEN,  W.  A.,  "Sir  William  Ramsay,  Memorials  of  His  Life  and  Work,"  Ref. 

(5),  p.  137. 

(13)  EULER,  H.  and  A.  EULER,  "Per  Theodor  Cleve,"  Ber.,  38,  4221-38   (Part  4, 

1905). 

(14)  TRAVERS,  M.  W.,  "The  Discovery  of  the  Rare  Gases,"  Ref.  (9),  pp.  90-1. 

(15)  RAMSAY,  W.,  "The  Gases  of  the  Atmosphere,"  Ref,  (2),  pp.  251-5. 

(16)  TRAVERS,  M.  W.,  "The  Discovery  of  the  Rare  Gases,"  Ref.  (9),  pp.  95-7. 

(17)  TILDEN,  W.  A.,  "Sir  William  Ramsay,  Memorials  of  His  Life  and  Work,"  Ref. 

(5),  P-  62. 

(18)  "Rare  gases  of  the  atmosphere.    A  classic  of  science,"  Sci  News  Letter,  18,  70-2 

(Aug.  2,  1930). 

(19)  RAMSAY,  W.,  "The  recently  discovered  gases  and  their  relation  to  the  periodic 

law,"  Science  [N.  S.],  9,  273-80  (Feb.  24,  1899);  Ber.,  31,  3111-21  (1898). 

(20)  YOUNG,  C.  A.,  "The  Sun,"  3rd  ed.,  D.  Appleton  and  Co.,  New  York  City,  1897, 

pp.  88-9,  259-60. 

(21)  Ibid.,  pp.  344-50. 

(22)  LOCKYER,  T.  MARY  and  WINIFRED  L.  LOCKYER,  "Life  and  Work  of  Sir  Norman 

Lockyer,"  Macmillan  and  Co.,  London,  1928,  474  pp. 

(23)  Ibid.,  pp.  155-7. 

(24)  Ibid.,  pp.  266-91. 

(25)  RAMSAY,  W.  and  W.  COLLIE,  "Helium  and  argon.     Part  III.     Experiments 

which  show  the  inactivity  of  these  elements,"  Nature,  54,  143  (June  11, 
1896);  Chem  News,  73,  259-60  (June  5,  1896). 

(26)  RAMSAY,  W.,  "The  position  of  argon  and  helium  among  the  elements,"  Chem, 

News,  73,  283  (June  19,  1896). 

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(28)  CROOKES,  W.,  "On  the  spectra  of  argon,"  Chem.  News,  71,  58-9   (Feb.  1, 

1895);  72,  66-9  (Aug.  9,  1895). 

(29)  CROOKES,  W.,  "The  spectrum  of  the  gas  from  cleveite,"  Chem.  News,  71,  151 

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(SO)  RAYLEIGH,  LORD  and  W.  RAMSAY,  "Argon:  A  new  constituent  of  the  atmos- 
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(81)  CLEVE,  P.  T.,  "On  the  presence  of  helium  in  cl&veite,"  Chem.  News,  71,  212 
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CLEVE,  P.  T.,  "Sur  la  densit<§  de  Thelium,"  Compt.  rend.,  120,  1212  (June  4, 
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THE  INERT  GASES  799 

(33)  REED,  "A  prediction  of  the  discovery  of  argon,"  Chem.  News,  71,  213-15  (May 

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(36)  JANSSEN,  P.-J.-C.,  "Indication  de  quelques-uns  des  resultats  obtenus  a  Guntoor 

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(37)  FRANKLAND,  E.  and  N.  LOCKYER,  "Recherches  sur  les  spectres  gazeux  dans 

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(39}     RAYLEIGH,  LORD,  "Letter  to  the  Editor,  Sept.  24,  1892,"  Nature,  46,  512-3 
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(40)  TRAVERS,  M.  W.,  "The  Discovery  of  the  Rare  Gases/'  Ref.  (9),  pp.  1-7. 

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(42)  "Scientific  worthies.    Lord  Rayleigh,"  Nature,  70,  361-3  (Aug.  18,  1904). 

(43)  MACPHERSON,  "Astronomers  of  Today,"  Gall  and  Inglis,  London,   1905,  pp. 

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800  DISCOVERY  OF  THE  ELEMENTS 

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(65)  DRAPER,  JOHN  W.,  "Science  in  America,"  Proc.  Am.  Chem.  Soc.,  Vol.  1,  Part  1, 

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(77)  GAUTIER,  A.,  "Observations  sur  la  nature  et  Torigine  des  gaz  qui  forment  les 

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applications  a  Teclairage  electrique  par  incandescence/*  La  Nature,  62  (2), 

90-1  (July  15,  1934). 
(82)     DUFRAISSE,  CH.,  "Charles  Moureu,"  Bull.  Soc.  Chim.  (Paris),  (4),  49,  741-825 

(1931);  NORRIS,  J.  F.,  J.  Am.  Chem.  Soc.,  52,  31-5  (May,  1930);  URBAIN, 

G.,  Ann.  chim.,  (10),  12,  3-8  (July,  Aug.,  1929). 


THE  INERT  GASES  801 

(83)  WRIGHT,  MILTON,  "Inventors  who  have  achieved  commercial  success,"  Sci.  Am., 

(2),  136,  396  (June,  1927);  J.  H.  O'NEIL,  "Purifying  gases  for  neon  signs/' 
Chem.  Met  Eng.,  36,  143-4  (Mar.,  1929);  GEORGES  CLAUDE,  "Progress  on 
luminous  tubes  containing  rare  gases,"  La  Nature,  1932,  Aug.  1,  pp.  121-3. 

(84)  "Necrology.    D.  F.  McFarland,"  Chem.  Eng.  News,  33,  1008  (Mar.  7,  1955). 

(85)  PROVENZAL,  GIULIO,  "Profili  Bio-Bibliografici  di  Chirnici  Italian!.     Sec.  XV- 

Sec.  XIX,"  Istituto  Nazionale  Medico  Farmacologico  "Serono"  Rome,  1937, 
pp.  257-70. 


Pierre  and  Marie  Curie 


Together,  this  famous  couple,  Pierre 
Curie,  1859-1906,  and  Mme.  Marie 
Sklodowska  Curie,  1867-1934,  dis- 
covered radium  and  polonium,  and 
founded  the  beneficent  science  of  ra- 
dioactivity. Pierre  served  as  professor 
of  physics  at  the  Sorbonne,  and  col- 
laborated with  his  brother,  Jacques 
Curie,  in  the  discovery  and  investiga- 
tion of  piezo-electricity.  He  intro- 
duced the  concept  of  symmetry  in 
physical  phenomena  and  studied  mag- 
netic properties  as  a  function  of  tem- 
perature. Marie  served  as  professor 
of  radioactivity  at  the  University  of 
Paris. 


"Radium  is  not  to  enrich  any  one.    It  is  an 
element;  it  is  for  all  people"  (I). 

"So  the  atoms  in  turn,  we  now  clearly  discern, 
Fly  to  bits  with  the  utmost  facility; 
They  wend  on  their  way,  and,  in  splitting,  display 
An  absolute  lack  of  stability"  (2) 


29 

The  natural  radioactive  elements 


In  1898  there  was  discovered  an  element,  radium,  which  con 
tinually  and  spontaneously  emits  light,  heat,  and  other  radiations. 
Investigation  of  these  astonishing  phenomena  by  the  Curies  and 
others  revealed  more  than  forty  interrelated  radioactive  ele- 
ments which,  like  radium,  are  unstable.  They  do  not,  however, 
occupy  forty  places  in  the  periodic  system,  but  are  crowded  into 
twelve  places.  The  explanation  for  the  existence  of  these  num- 
erous so-called  "radioactive  isotopes"  and  their  genealogical 
descent  from  uranium  and  thorium  were  discovered  independ- 
ently by  K.  Fajans,  F.  Soddy,  A.  S.  Russell,  and  A.  Fleck.  Since 
the  original  literature  on  the  radioactive  elements  embraces  such 
a  vast  field  of  research,  the  following  account  of  their  discovery 
is  necessarily  far  from  complete. 


A 


[ntoine-Henri  Becquerel,  a  member  of  a  family  renowned  for 
scientific  achievement,  noticed  in  1896  that  when  a  phosphorescent  salt, 
such  as  potassium  uranyl  sulfate,  is  placed  near  a  photographic  plate 
protected  by  black  paper,  the  plate  becomes  fogged  as  though  it  had  been 
exposed  to  light  (51,  58).  His  later  work  showed  that  all  uranium  com- 
pounds, even  those  which  do  not  phosphoresce,  give  off  penetrating  rays 
which,  like  X-rays,  darken  a  photographic  plate  and,  by  making  the 
surrounding  air  a  conductor,  cause  the  gold  leaves  of  a  charged  electro- 
scope to  lose  their  electrostatic  charge  and  collapse.  These  radiations 
are  now  known  to  be  of  three  kinds:  alpha  rays,  which  consist  of  helium 
atoms  each  bearing  two  units  of  positive  electricity;  beta  rays  consisting 
of  streams  of  negative  electrons;  and  gamma  rays,  which  constitute  a 
very  penetrating  radiation  of  extremely  short  wave  length. 

The  amazingly  rapid  development  of  the  science  of  radioactivity  is 
largely  due  to  the  brilliant  work  of  M.  Pierre  Curie  and  his  wife,  Mme. 
Marie  Sklodowska  Curie.  The  former  was  born  in  Paris  on  May  15, 
1859,  and  was  educated  by  his  cultured  parents.  Many  happy  hours 
were  spent  on  excursions  to  the  country.,  and  thus  this  city  child  grew  up 
in  intimate  contact  with  nature,  collecting  plants  and  animals  and  enjoy- 
ing them  in  quiet  contemplation.  While  serving  as  director  of  the 
laboratory  under  Paul  Schutzenberger  at  the  School  of  Physics  and  Chem- 

803 


804  DISCOVERY  OF   THE  ELEMENTS 

istry,  Pierre  Curie  carried  on  researches  on  condensers,  magnetism,  piezo- 
electricity, and  the  principle  of  symmetry  in  nature.  When  in  1895  he 
received  the  degree  of  Docteur-es-sciences  from  the  Sorbonne,  Schiitzen- 
berger  created  a  chair  of  physics  for  him  (3). 

Marie  Sklodowska,  a  daughter  of  Dr.  Sklodowski,*  a  professor  of 
physics  and  mathematics  at  the  Warsaw  gymnasium,  was  born  on 
November  7,  1867.  Because  of  the  early  death  of  her  gifted  mother,  the 
little  girl  grew  up  in  her  father's  laboratory  and  under  his  instruction. 
She  soon  developed  a  passionate  love  of  country  and  joined  a  secret 
society  of  students  who  organized  evening  classes  for  laborers  and 
peasants.  However,  because  of  the  limited  opportunities  for  advanced 
study,  she  decided  to  leave  her  beloved  motherland  and  go  to  Paris  (99). 


Antoine-Henri      Becquerel,      1852-1908. 

French  physicist  and  engineer.  Discov- 
erer of  die  rays  emitted  by  uranium.  He 
carried  out  important  researches  on  rota- 
tory magnetic  polarization,  phosphores- 
cence, infrared  spectra,  and  radioactivity. 
His  grandfather  Antoine-Cesar-Becquerel 
(1788-1878),  and  his  father,  Alexandre- 
Edmond  Becquerel  (1820-1891),  also 
made  many  important  contributions  to 
chemistry  and  physics. 


During  the  four  years  of  her  student  life,  she  lived  in  a  chilly  little 
attic  room,  carrying  the  coal  herself  up  the  six  flights  of  stairs,  and  cooking 
her  simple  meals  over  an  alcohol  lamp.  This  was  Marie  Sklodowska's 
introduction  to  the  city  which  became  her  permanent  home  (4,  68). 
When  she  enrolled  at  the  Sorbonne,  Henri  Poincare,  the  famous  mathe- 
matical physicist,  soon  recognized  her  ability,  and  Professor  Gabriel 
Lippmann  also  took  great  interest  in  her  research. 

Her  first  meeting  with  Pierre  Curie  was  at  the  home  of  a  Polish 
physicist  in  Paris.  Because  of  their  mutual  interest  in  scientific,  social, 
and  humanitarian  subjects,  there  gradually  developed  a  singleness  of 

*  The  feminine  ends  in  -ska,  the  masculine  in  -ski. 


THE  NATURAL  RADIOACTIVE  ELEMENTS 


805 


(Jules)     Henri    Poincare,    1854W912. 

French  mathematician,  physicist,  and 
astronomer.  Prolific  and  gifted  writer 
on  mathematical  analysis,  analytical  and 
celestial  mechanics,  mathematical  phys- 
ics, and  philosophy  of  science. 


Gabriel  Lippmann.,  1845-1921.  Profes- 
sor of  mathematical  physics  at  the  Uni- 
versity of  Paris.  Inventor  of  the  capil- 
lary electrometer  and  of  a  process  of 
direct  color  photography.  The  phenome- 
non of  piezo-electricity  in  crystals  pre- 
dicted by  Professor  Lippmann  was  first 
demonstrated  experimentally  by  Pierre 
and  Jacques  Curie. 


purpose  that  caused  M.  Curie  to  say,  "It  would  ...  be  a  beautiful  thing 
in  which  I  hardly  dare  believe,  to  pass  through  life  together  hypnotized 
in  our  dreams:  your  dream  for  your  country;  our  dream  for  humanity; 
our  dream  for  science."  After  their  marriage  in  1895  Professor  Schutzen- 
berger  arranged  that  they  might  work  together  in  the  laboratory,  and 


806  DISCOVERY  OF  THE  ELEMENTS 

their  mutual  devotion  to  science  once  led  M.  Curie  to  remark,  "I  have  got 
a  wife  made  expressly  for  me  to  share  all  my  preoccupations"  (5). 

George  Jaffe,  who  carried  out  laboratory  research  under  Pierre  and 
Marie  Curie,  wrote  "There  have  been,  and  there  are,  scientific  couples 
who  collaborate  with  great  distinction,  but  there  has  not  been  a  second 
union  of  woman  and  man  who  represented,  both  in  their  own  right,  a 
great  scientist.  Nor  would  it  be  possible  to  find  a  more  distinguished 
instance  where  husband  and  wife  with  all  their  mutual  admiration  and 
devotion  preserved  so  completely  independence  of  character,  in  life  as 
well  as  in  science"  (113). 

POLONIUM 

Professor  Curie  continued  his  researches  on  the  growth  of  crystals, 
and  his  young  wife  prepared  for  her  examinations.  Many  chemists  con- 
sider her  dissertation  (55)  to  be  the  most  remarkable  thesis  ever  presented 
for  the  doctorate.  She  continued  the  work  begun  by  Becquerel,  and 
tested  most  of  the  known  elements,  including  a  number  of  rare  ones 
loaned  by  E.-A.  Demar^ay  and  Georges  Urbain,  with  Prof.  Curie's  piezo- 
electric quartz  electrometer,  and  found  that  thorium  and  uranium  were 
the  only  ones  whose  compounds  produced  appreciable  ionization  (26,  54, 
55).  The  radioactivity  of  thorium  was  discovered  independently  by 
Gerhardt  Carl  Schmidt,  professor  of  physics  at  the  University  of 
Miinster  (25). 

Of  much  greater  significance  than  this,  however,  was  Mme.  Curie's 
observation  that  the  activity  of  the  uranium  mineral  pitchblende  is  four 
or  five  times  as  great  as  one  might  expect  it  to  be  from  its  uranium 
content  (24).  She  concluded  that  the  ore  must  contain  another  radio- 
active element  in  addition  to  uranium,  and  that,  since  the  composition  of 
the  ore  was  known,  the  active  element  must  be  present  in  extremely 
smaU  amount  and  must  therefore  be  very  active  indeed.  Therefore  it 
became  necessary  to  work  up  large  quantities  of  pitchblende  and  to  make 
elaborate  and  tedious  fractionations  of  this  complex  ore. 

The  pitchblende  was  supplied  by  the  Austrian  government  from  its 
uranium  mines  in  the  Joachimsthal,  Bohemia.  Mme.  Curie  explained  that 
pitchblende  was  so  expensive  that  they  were  unable  to  buy  enough  of  it 
for  their  large-scale  researches.  Since  the  residues  from  the  St.  Joa- 
chimsthal uranium  mine  had  not  previously  been  put  to  use,  M.  and  Mme. 
Curie,  through  the  influence  of  the  Academy  of  Sciences  of  Vienna,  were 
able  to  obtain  several  tons  of  these  residues  at  a  moderate  price  (114). 

As  Mme.  Curie  examined  each  fraction  with  the  electrometer,  she 
found  that  a  very  active  substance  separated  with  the  bismuth.  After 
convincing  herself  in  1898  that  this  was  a  new  element,  she  named  it 


THE  NATURAL  RADIOACTIVE  ELEMENTS  807 


FACULTY  DES  SCIENCES  DE  PARIS 

y 

............  .I 


INSTITCT  DU   HAD1UM 


0 
**  JLf 


tA00RATOJ«E  CUBIC 
1,  Rue  Pierre-Curie,  Paris  (5*) 


&*JL^-^ 


^ 

t^S* S&&&*  **€<^es&*~r  * 


Edgar  FaTw  Sm«7z  Memorial  Collection,  University  o/ 
Autograph  Letter  from  Mme.  Curie  to  Dr.  Edgar  F.  Smith 


808 


DISCOVERY  OF  THE  ELEMENTS 


polonium  in  honor  of  her  native  country  (27,  65).  It  is  also  known  as 
radium  F.  In  1902  Dr.  Willy  Marckwald  of  Berlin  obtained  a  metallic 
deposit  on  a  polished  plate  of  bismuth  immersed  in  a  solution  of  the 
bismuth  fraction  from  pitchblende.  This  deposit,  which  he  called  radio- 
tellurium,  was  later  shown  to  be  identical  with  Mme.  Curie's  polonium 
(6,  29). 


THE  NATURAL  RADIOACTIVE  ELEMENTS  809 

After  commenting  on  the  discovery  of  gallium,  scandium,  and  ger- 
manium (eka-aluminum,  eka-boron,  and  eka-silicon),  D.  I.  Mendeleev  had 
written  in  1891,  "I  foresee  some  more  new  elements,  but  not  with  the  same 
certitude  as  before.  I  shall  give  one  example,  and  yet  I  do  not  see  it 
quite  distinctly"  ( 7) .  He  had  then  proceeded  to  describe  an  undiscovered 
"dvi  tellurium"  with  an  atomic  weight  of  about  212.  Since  polonium 
resembles  tellurium  and  has  an  estimated  atomic  weight  of  about  210, 
it  is  probably  the  realization  of  Mendeleev's  "dvi  tellurium." 

A  Non-radioactive  Isotope  of  Polonium.  In  an  examination  of  the 
X-ray  spectra  of  the  gold-tellurium  minerals  of  Transylvania,  Professor 
Horia  Hulubei  and  Mile.  Yvette  Cauchois  discovered  the  existence  of 
a  non-radioactive  isotope  of  polonium  (element  84)  (115).  The  ore 
they  examined  contained  (in  addition  to  the  principal  constituents: 
gold,  lead,  and  tellurium)  silver,  arsenic,  antimony,  copper,  nickel,  zinc, 
sulfur,  and  a  trace  of  selenium.  After  dissolving  the  ore  and  removing 
most  of  the  gold,  silver,  and  lead  as  chlorides,  element  84  ( along  with 
other  elements)  was  deposited  electrochemically  on  silver.  After  dis- 
solving the  deposit  and  removing  the  silver  by  precipitation,  Professor 
Hulubei  and  Mile.  Cauchois  placed  the  remaining  salts  on  an  anticathode 
and  subjected  them  to  X-ray  analysis  with  their  curved-crystal  focusing 
spectrograph  (115).  In  this  non-radioactive  material  they  observed  the 
lines  of  element  84,  polonium.  They  estimated  that  the  new  isotope 
of  polonium  must  be  present  in  their  sample  in  the  proportion  of  about 
one  part  in  a  million. 

RADIUM 

After  the  Curies,  with  the  assistance  of  M.  G.  Bemont,  had  carried 
out  many  laborious  fractionations  of  barium  chloride,  they  found  that 
the  most  insoluble  fractions  were  the  most  radioactive.  In  the  course  of 
her  experiments  Mme.  Curie  had  learned  that  radioactivity  is  an  atomic 
property  depending  solely  on  the  quantity  of  active  element  present." 
For  this  reason  the  presence  of  another  active  element  was  suspected, 
and  the  radioactive  barium  chloride  was  therefore  submitted  to  M. 
Demargay  for  spectroscopic  examination.  He  detected  a  new  line  in 
the  ultraviolet  region  of  the  spectrum,  and  certain  other  lines,  all  of 
which  were  most  distinct  in  the  most  radioactive  preparations,  and,  as 
fractionation  proceeded,  the  barium  lines  became  fainter  and  fainter 
(23,28,52). 

J  While  tracing  down  the  new  element,  the  Curies  often  wondered 
how  its  salts  would  look,  and  hoped  that  perhaps  they  might  display 
beautiful  colors.  The  radium  chloride  which  they  finally  obtained  proved 
to  be  a  white  salt,  however,  but  it  was  even  more  beautiful  than  their 


810  DISCOVEEY  OF  THE  ELEMENTS 

brightest  dreams:  it  glowed  in  the  dark!  j  Radium,  like  phosphorus,  is 
a  giver  of  light,  and  this  property  was  to  fliem,  as  it  had  been  to^Hennig 
Brand  and  Johann  Kunckel,  a  source  of  surprise  and  delight.  "One  of 
our  joys,"  wrote  Mme.  Curie,  "was  to  go  into  our  workroom  at  night; 
we  then  perceived  on  all  sides  the  feebly  luminous  silhouettes  of  the 
bottles  or  capsules  containing  our  products.  It  was  really  a  lovely  sight 
and  always  new  to  us.  The  glowing  tubes  looked  like  faint  fairy  lights" 
(8,60). 


The  Laboratory*  in  which  M.  and  Mme.  Curie  discovered  radium 


!*  The  new  substance  was  named  radium,  the  giver  of  rays,  and,  were  it 
not  for  this  property,  it  might  still  be  numbered  among  the  missing 
elements.  Although  it  gives  a  distinct  spectrum,  the  methods  of  detecting 
it  with  an  electrometer  is  five  hundred  thousand  times  more  sensitive 
than  the  spectroscopic  method!1  (9). 

Professor  Georges  Urbain  once  said: 

I  was  certainly  privileged,  for  I  saw  with  my  own  eyes  the  birth  of  radium. 
Pierre  Curie,  who  was  my  teacher,  rendered  me  the  incomparable  honor  of 
according  me  his  confidence  and  friendship.  I  saw  Mme.  Curie  work  like  a 
man  at  the  difficult  treatments  of  great  quantities  of  pitchblende.  I  saw  the 
first  fractionations  of  the  bromides  of  barium-radium.  I  saw  the  radium- 
bearing  crystals  shine  in  the  dark  before  the  radium  spectrum  could  be  ob- 
served in  them.  Every  Sunday  we  used  to  go  with  Langevin,  Perrin,  Debierne, 

*  Reproduced  from  an  article  hy  Jacques  Danne,  La  Nature,  32  [1],  217  (Mar.  5, 
1904)  by  permission  of  Masson  et  Cie.,  Paris. 


THE  NATURAL  RADIOACTIVE  ELEMENTS  811 

Cotton,  and  Sagnac  to  the  little  Curie  home,  which  was  thus  transformed  into 
an  intimate  academy.  There  the  master,  with  his  customary  simplicity,  ex- 
plained his  ideas  to  us  and  deigned  to  discuss  ours.  .  .  .  (74). 

Wilhelm  Ostwald  (112)  gave  in  his  autobiography  the  following 
account  of  his  visit  to  the  birthplace  of  radium: 

At  my  urgent  request  the  Curie  laboratory,  in  which  radium  was  dis- 
covered a  short  time  ago,  was  shown  to  me.  The  Curies  themselves  were 
traveling.  It  was  a  cross  between  a  horse-stable  and  a  potato-cellar,  and,  if  I 
had  not  seen  the  worktable  with  the  chemical  apparatus,  I  would  have  thought 
it  a  practical  joke  (10) . 

When  M.  Curie  was  offered  the  decoration  of  the  Legion  of  Honor, 
he  wrote,  "I  pray  you  to  thank  the  Minister,  and  to  inform  him  that  I 
do  not  in  the  least  feel  the  need  of  a  decoration,  but  that  I  do  feel  the 
greatest  need  for  a  laboratory."  Nevertheless,  Mme.  Curie  regarded  the 
years  spent  in  this  dingy  old  shed  as  "the  best  and  happiest"  of  her 
life  (8). 

THE  URANIUM  SERIES 

In  1900  Sir  William  Crookes  prepared  a  solution  containing  a 
uranium  salt  and  a  small  amount  of  a  ferric  salt.  When  he  added  to 
this  an  excess  of  a  solution  containing  ammonium  hydroxide  and  am- 
monium carbonate,  he  found  that  the  resulting  ferric  hydroxide  precipi- 
tate was  intensely  radioactive.  After  studying  the  radioactive  properties 
of  the  substance  which  precipitates  with  the  iron,  he  said,  "For  the  sake 
of  lucidity  the  new  body  must  have  a  name.  Until  it  is  more  tractable 
I  will  call  it  provisionally  UrX— the  unknown  substance  in  uranium" 
(30).  It  is  now  known  as  uranium  XL.  H.  N.  McCoy  and  W.  H.  Ross, 
B.  B.  Boltwood,  and  R.  B.  Moore  and  H.  Schlundt  found  independently 
that  there  are  two  uraniums,  uranium  1  and  uranium  2  (12,  48,  81,  108, 
109,110}. 

In  1913  Kasimir  Fajans  and  O.  H.  Gohring  of  Karlsruhe  showed  that 
uranium  Xi  disintegrates  by  /3-ray  emission  into  a  very  short-lived  product 
which  they  called  brevium  (11,  48),  but  which  is  now  known  as  uramum 
X2.  Professor  Fajans  taught  physical  chemistry  for  many  years  at  the 
University  of  Munich  and  is  now  teaching  at  the  University  of  Michigan 
(70).  Like  Mme.  Curie  he  is  a  native  of  Warsaw.  Mendeleev  predicted 
the  discoveiy  of  uranium  X2  in  1871  when  he  said,  "There  is  a  third 
vacant  place  at  series  12  in  group  V  between  Th  ~  231  and  U  =  240 
for  an  element  which  forms  [the  oxide]  R2O5  and  has  an  atomic  weight 
of  about  235"  (71). 

Since  uranium  Xx  gives  two  kinds  of  ft-rays,  it  yields  two  radioactive 


812 


DISCOVERY  OF  THE  ELEMENTS 


products:  uranium  X2  and  uranium  Z  (12).  The  latter  substance, 
which  was  discovered  by  Professor  Otto  Hahn  in  1921,  is  a  subordinate 
branch  of  the  family,  however,  for  the  disintegration  of  uranium  Xj. 
yields  99.65  per  cent  of  uranium  X2  and  only  0.35  per  cent  of  uranium  Z. 
Professor  Hahn  is  a  native  of  Frankfort-on-the  Main.  He  collabo- 
rated with  Sir  William  Ramsay,  and  later  with  Miss  Lise  Meitner,  and 
in  1944  was  awarded  the  Nobel  Prize  in  Chemistry  for  his  work  on 
atomic  fission.  He  is  a  member  of  the  German  Atomic  Weight  Com- 
mission and  director  of  the  Kaiser  Wilhelm  Institute  for  Chemistry  in 
Berlin-Dahlem.  Miss  Meitner,  who  was  also  on  the  staff  of  this  Insti- 
tute, is  a  native  of  Vienna. 


Kasimir  Fajans,  1887—  .  American 
physical  chemist,  born  in  Poland.  Pro- 
fessor at  the  University  of  Michigan. 
Codiscoverer  with  Gohring  of  uranium 
X2  (brevium).  In  1913  he  discovered, 
simultaneously  with  Soddy,  the  law  of 
radioactive  displacement  of  elements  in 
the  periodic  system  as  the  result  of 
a-  and  /3-ray  emission. 


Courtesy    Cornell    University 


There  is  also  a  sixth  member  of  this  series,  known  as  uranium  Y 
(46,  50,  56,  59),  which  was  discovered  in  1911  by  G.  N.  Antonoff,  who 
was  working  under  Sir  Ernest  Rutherford  at  the  University  of  Man- 
chester. He  afterward  returned  to  St.  Petersburg.  Uranium  Y,  like 
uranium  Z,  belongs  to  a  subordinate  branch  of  the  family.  Frederick 
Soddy  attributed  AntonofFs  success,  not  to  the  special  chemical  process 
adopted,  but  "to  the  lapse  of  a  suitable  period  of  time  between  succes- 
sive separations"  (75).  Thus  in  the  uranium  series  uranium  1  breaks 
down  to  form  uranium  X1?  and  this  in  turn  disintegrates  to  form  the 
successive  products:  uranium  X2,  uranium  Z,  uranium  2,  and  uranium  Y. 


THE  NATURAL  RADIOACTIVE  ELEMENTS 


813 


THE  RADIUM  SERIES 

In  1904  B.  B.  Boltwood,  H.  N.  McCoy,  and  R.  J.  Strutt  proved  inde- 
pendently that  radium  is  produced  by  spontaneous  transmutation  of 
uranium  (107).  Three  years  later  Boltwood  discovered  an  element  which 
he  named  ionium  and  which  he  found  to  be  the  parent  substance  of 
radium  (39).  Professor  Boltwood  had  acquired  a  broad  cosmopolitan 
education  in  Munich,  Leipzig,  Manchester,  and  New  Haven,  and  was 
a  skilled  laboratory  technician,  a  sympathetic  teacher,  and  a  polished 
gentleman  with  "a  certain  courtliness  of  manner."  He  proved  that  there  is 
a  genetic  relationship  between  uranium,  ionium,  and  radium  (13). 
Ionium  was  discovered  independently  at  about  the  same  time  by  Otto 
Hahn  and  by  Willy  Marckwald  (14,  73,  77). 


Bertram   Borden   Boltwood,    1870-1927. 

Professor  of  chemistry  and  physics  at 
Yale  University.  Discoverer  of  the  radio- 
active element  ionium,  the  parent  of  ra- 
dium. Ionium  was  discovered  independ- 
ently at  about  the  same  time  by  Hahn 
and  by  Marckwald. 


The  Edgar  F.   Smith  Memorial  Collection, 
University   of  Pennsylvania 


The  second  member  of  the  series  is  radium  itself.  The  task  of  iso- 
lating it  was  most  difficult,  and  involved  risk  of  losing  the  precious 
product.  In  1910,  however,  Mme.  Curie  and  M.  Andre  Debierne  finally 
succeeded  in  preparing  the  shining  white  metal;  but,  since  they  needed 
the  radium  in  their  researches,  they  did  not  keep  it  in  this  form. 

Like  all  radioactive  elements,  it  undergoes  continuous,  spontaneous 
disintegration  into  elements  of  lower  atomic  weight.  M.  and  Mme.  Curie 
had  noticed  that  when  air  comes  into  contact  with  radium  compounds  it, 
too,  becomes  radioactive.  The  correct  explanation  was  first  given  in 


814  DISCOVERY  OF  THE  ELEMENTS 


Condensation  of  the  Radium  Emanation  on  the  occasion  of  Professor  Cox's 
lecture  on  liquid  air  in  the  Macdonald  Physics  Building  at  McGill  Univer- 
sity, Nov.  6,  1902.  The  original  coil  of  Rutherford  and  Soddy  which  appears 
in  this  picture  and  in  which  the  first  condensation  was  effected  is  still  in  the 
Physics  Building  at  McGill  University.  The  original  photograph  bears  the 
initials  F.  S.  [Soddy].*  It  was  in  the  Macdonald  Physics  Building  that 
Rutherford  and  Soddy  proved  that  the  radioactive  elements  undergo 
spontaneous  transformation.  See  also  ref.  (138). 

1900  by  Friedrich  Ernst  Dorn,  who  was  born  on  July  27,  1848,  at 
Guttstadt  in  eastern  Prussia.  He  studied  at  Konigsberg  and  taught  physics 
for  many  years  at  Darmstadt  and  at  Halle.  Professor  Dorn  showed  that 
one  of  the  disintegration  products  of  radium  is  a  gas  (15,  37).  This  was 
at  first  called  radium  emanation,  or  niton,  but,  since  it  is  an  inert  gas 
derived  from  radium  the  modern  name  radon  is  to  be  preferred.  After 
showing  that  the  highest  temperatures  obtainable  had  no  effect  on  the 
rate  of  transformation  of  this  emanation,  Rutherford  and  Soddy  decided 
to  try  the  effect  of  extreme  cold.  According  to  Professor  A.  S.  Eve, 
"Within  a  quarter  of  an  hour  after  the  first  100  cc.  of  liquid  air  were 
prepared,  the  emanation  had  been  condensed,  and  the  material  nature  of 
this  gas  had  been  proved  beyond  question"  (103).  It  is  the  last  mem- 

*  The  writer  wishes  to  thank  Dr.  William  H.  Barnes  and  Dr.  A.  S.  Eve  of  McGill 

University  for  their  kind  assistance  in  procuring  the  photograph  of  the  apparatus  for 

condensing  radon  and  the  portraits  of  Miss  Brooks   (Mrs.  Pitcher)    (p.  815)   and 

Professor  Owens  (p.  826). 


THE  NATURAL  RADIOACTIVE  ELEMENTS 


815 


her  of  the  group  of  noble  gases  previously  discovered  by  Sir  William 
Ramsay  (62),  and  in  1910  the  remarkable  density  determination  of 
Ramsay  and  Robert  Whytlaw  Gray  proved  that  it  is  the  heaviest  gas 
known  (91). 

In  1904  Miss  Harriet  Brooks  of  McGill  University  in  Montreal  studied 
the  "active  deposit  of  short  life"  which  forms  as  a  thin  layer  on  all 
substances  which  have  been  exposed  to  radon  (43),  a  phenomenon  which 
Soddy  compared  to  "a  sort  of  continuous  snowstorm  silently  going  on 
covering  every  available  surface  with  this  invisible,  unweighable,  but 
intensely  radioactive  deposit"  (83).  From  Miss  Brooks's  researches  and 


Harriet  Brooks,  1876-1933  (Mrs.  Frank 
Pitcher).  In  1902  Rutherford  and  Miss 
Brooks  studied  the  penetrating  power 
of  a-rays  from  various  sources  and  made 
the  first  attempt  to  determine  the  den- 
sity of  radon  by  a  diffusion  method. 
Their  study  led  to  the  discovery  of  ra- 
dium A,  B,  and  C.  This  photograph 
was  taken  in  1898  when  Miss  Brooks 
obtained  her  B.A.,  McGill  University. 


Photo  by  William  Notman  6-  Son,  Ltd. 


his  own,  Rutherford  concluded  that  radon  forms  three  successive  disinte- 
gration products:  radium  A,  B,  and  C.  These  were  found  and  separated, 
and  in  "the  active  deposit  of  long  life"  there  were  discovered  three  addi- 
tional elements:  radium  D,  E,  and  F  (polonium),  which  are  products 
of  further  disintegration  (11,  53). 

Sir  Ernest  Rutherford  was  born  in  1871  in  Nelson,  New  Zealand. 
After  studying  at  New  Zealand  University  and  Cambridge,  he  went  to 
Canada  in  1898  as  a  professor  of  physics  at  McGill  University.  After 
serving  there  for  nine  years  and  carrying  out  many  remarkable  researches 
in  radioactivity,  he  became  professor  of  physics  at  Manchester  Uni- 
versity, and  in  the  following  year  he  was  awarded  the  Nobel  Prize  in 
chemistry.  In  1919  he  became  a  professor  at  Cambridge  (72). 


816 


DISCOVERY  OF  THE  ELEMENTS 


Lord  Rutherford,   1871-1937. 

Professor  of  physics  at  MoGill, 
Manchester,  and  Cambridge 
Universities.  He  identified 
the  three  types  of  radiations 
from  radioactive  substances, 
and  devised  methods  for 
counting  alpha  particles  and 
for  determining  the  number 
of  free  positive  electrons  in 
the  nucleus  of  an  atom. 


Courtesy  Mr.   Sederholm,  Nobelstiftelsen,  Stockholm 

His  three  greatest  discoveries  were  the  proof  of  the  transmutation 
of  radium  into  other  elements  (Rutherford  and  Soddy),  the  nuclear 
atom,  and  artificial  transmutation.  Lord  Rutherford  took  his  teaching 
duties  very  seriously  and  was  exceedingly  kind  to  his  students  and 
collaborators  and  most  generous  in  sharing  with  them  his  ideas  and  his 
honors.  Because  of  his  remarkable  genius  for  planning  research  and 
apportioning  to  every  worker  a  task  suited  to  his  ability,  he  trained 
many  of  the  physicists  and  chemists  who  are  now  working  in  the  great 
research  institutes  throughout  the  world  (104). 

Professor  H.  Geiger  stated  that  Lord  Rutherford  "threatened  the 
severest  penalties"  for  anyone  who  allowed  emanation  to  escape,  for  it 
spread  rapidly  throughout  the  building  and  made  it  impossible  to  work 
with  the  electroscope.  One  day  when  Geiger's  counting  experiments  were 
thus  interrupted,  he  found  that  the  emanation  was  coming  from  the  room 
where  Rutherford  was  working.  When  informed  of  the  trouble,  Ruther- 
ford replied,  "Well,  there  you  have  further  proof  of  the  power  inherent 
in  this  emanation."  Thereupon  he  took  Dr.  Geiger  for  a  ride  in  the 
country  and  "was  soon  discoursing  on  his  own  experiments  and  on  all 
the  problems  that  were  yet  to  be  solved.  Nothing  was  so  refreshing  nor 


THE  NATURAL  RADIOACTIVE  ELEMENTS  817 


Courtesy    Ralph    E.    Oesper 

Otto  Honigschmid,  1878-  .  Director  of  the  German  Atomic  Weight 
Laboratory  at  the  University  of  Munich.  At  the  Radium  Institute  in 
Vienna  he  made  the  first  accurate  determination  of  the  atomic  weight  of 
radium.  His  work  on  radioactive  elements  strikingly  confirmed  the 
hypothesis  of  atomic  disintegration  proposed  by  Rutherford  and  Soddy. 

Seeref.  (135). 


818  DISCOVERY  OF  THE  ELEMENTS 

so  inspiring  as  to  spend  an  hour  in  this  way,  alone  with  Rutherford"  (102 ). 

According  to  J.  J.  Thomson,  Lord  Rutherford's  death  on  October  19, 
1937,  "just  on  the  eve  of  his  having  in  the  High-Tension  Laboratory  means 
of  research  far  more  powerful  than  those  with  which  he  had  already 
obtained  results  of  profound  importance,  is,  I  think,  one  of  the  greatest 
tragedies  in  the  history  of  Science"  (101,  102).  Lord  Rutherford  was 
the  first  scientist  born  in  the  overseas  dominions  to  be  buried  in  West- 
minster Abbey,  beside  the  graves  of  Sir  Isaac  Newton,  Lord  Kelvin, 
Charles  Darwin,  and  Sir  John  Herschel. 

Hahn  and  Meitner  (82)  and  Fajans  (33)  found  that  radium  C 
disintegrates  in  two  ways,  forming  radium  C'  and  radium  C".  K.  A. 
Hofmann  and  Eduard  Strauss  noticed  in  1900  that  radium  D  has  a 
strong  resemblance  to  lead,  and  these  two  elements  were  later  found  to 
be  inseparable  (38).  Karl  A.  Hofmann  was  associated  with  Adolf 
Baeyer  at  Munich. 

Elster  and  Geitel  also  made  pioneer  researches  on  "radio-lead,"  of 
which  radium  D  is  the  principal  constituent  (42}. 

Julius  Elster  was  born  on  December  24,  1854,  at  Blankenburg,  Ger- 
many (85),  and  studied  at  Berlin  and  Heidelberg.  In  1881  he  began  his 
teaching  career  at  the  Wolfenbiittel  Gymnasium,  where  he  was  destined 
to  serve  for  nearly  forty  years  and  to  carry  out  many  brilliant  researches 
with  his  intimate  friend,  Hans  F.  K.  Geitel  (1855-1923).  They  showed 
that  the  radioactivity  of  common  lead  is  not  a  specific  property  of  the 
element,  but  that  it  is  always  caused  by  admixture  of  some  radioactive 
substance.  Very  old  specimens  of  lead,  which  no  longer  contain  radium 
D,  are  inactive  (85).  The  friendship  of  Elster  and  Geitel  lasted  from 
childhood  throughout  life.  During  their  first  years  at  Wolfenbiittel,  they 
lived  with  Geitel's  mother.  After  her  death,  Elster  married,  and  built 
a  fine,  hospitable  home  and  private  laboratory,  where  Geitel  became  a 
permanent  member  of  the  household  and  where  they  prepared  more  than 
a  hundred  joint  papers.  Together  they  proved  that  the  electrical  con- 
ductivity of  the  atmosphere  is  not  caused  by  dust  but  by  ions  produced  by 
radioactive  substances  present  in  the  air.  They  also  demonstrated  the 
surprisingly  wide  distribution  of  radioactive  substances.  Simultaneously 
with  Sir  William  Crookes,  they  observed  the  scintillations  of  Sidot  blende 
when  bombarded  with  alpha  particles.  As  early  as  1899  they  recognized 
that  the  atom  of  a  radioactive  element  is  unstable  and  that  it  gradually 
breaks  down  into  the  stable  atom  of  an  inactive  element.  Since  Elster 
and  Geitel  were  of  almost  the  same  age  and  since  their  names  are 
inseparable,  German  physicists  chose  an  intermediate  date  for  the  ob- 
servance of  their  sixtieth  birthday  (96,  106).  Professor  Elster  died  at 
Wolfenbiittel  on  April  8,  1920  (96). 

Ramsay,  Soddy,  Fajans,  and  Georg  Bredig  were  all  greatly  interested 


THE  NATURAL  RADIOACTIVE  ELEMENTS 


819 


Theodore  William  Richards,  1868- 
1928.  Director  of  the  Wolcott  Gibbs 
Memorial  Laboratory  at  Harvard  Uni- 
versity. The  precision  of  his  atomic 
weight  determinations  has  never  been 
surpassed.  He  discovered  the  anoma- 
lous atomic  weights  of  lead  from  radio- 
active minerals. 


Courtesy    Harvard    University 


in  the  anomalous  atomic  weights  of  lead  from  various  sources,  and 
Fajans  sent  his  assistant,  Max  E.  Lembert,  to  America  to  work  on  this 
problem  with  Theodore  William  Richards  at  Harvard  (67,  78).  Fajans 
also  provided  Professor  Richards  with  several  radioactive  ores  containing 
lead.  After  studying  ores  from  Ceylon,  Colorado,  England,  Norway,  and 
Bohemia,  Richards  and  Lembert  announced  in  1914  that  the  atomic  weight 
of  lead  from  such  minerals  is  much  lower  than  207,2,  the  value  accepted 
for  ordinary  lead  (16,  78,  87).  O.  Honigschmid  and  Mile.  Stephanie 
Horovitz  (79)  of  Vienna  and  Maurice  Curie  (92)  made  the  same  dis- 
covery independently  at  about  the  same  time. 

These  two  kinds  of  lead  are  now  known  to  be  isotopes,  or  inseparable 
elements  which  belong  in  the  same  space  in  the  -periodic  table  and  yet 
differ  in  atomic  weight  and  in  radioactive  properties.  According  to 
Frederick  Soddy,  the  first  clear  recognition  of  isotopes  as  chemically 
inseparable  substances  was  that  of  H.  N.  McCoy  and  W.  H.  Ross  in  1907 
(75, 107).  Strictly  speaking,  the  science  of  radioactivity  has  revealed  only 
five  naturally  occurring  new  elements  with  distinctive  physical  and 
chemical  properties:  polonium,  thoron,  radium,  actinium,  and  uranium 
X2.  All  the  other  natural  "radioactive  elements"  share  previously  occu- 
pied places  in  the  periodic  table. 

Since  the  activity  of  polonium  in  time  disappears  completely,  and 
since  the  ratio  of  lead  to  uranium  is  almost  constant  in  all  primary 
uranium  minerals  from  a  given  geological  formation,  the  last  stage  in  the 


820  DISCOVERY  OF  THE  ELEMENTS 

disintegration  of  uranium  is  believed  to  be  a  stable  element,  uraniolead 
or  radium  G,  which  is  inseparable  from  ordinary  lead.  The  members  of 
the  radium  series  are:  ionium,  radium,  radon,  and  radium  A,  B,  C,  C , 
C",  D,  E,  F,  and  G. 

THE  ACTINIUM  SERIES 

F.  Soddy,  A.  S.  Russell,  and  K.  Fajans  independently  predicted  the 
existence  of  a'new  member  of  the  uranium  series  of  radioactive  elements 
and  that  it  would  occupy  the  vacant  place  just  below  tantalum  in  the  Va 
group  of  the  periodic  system.  Protactinium,  the  patriarch  of  the  actinium 
series  of  elements,  was  discovered  in  1917  independently  by  Otto  Hahn 
and  Miss  Lise  Meitner,  by  K.  Fajans,  and  by  Frederick  Soddy,  John  A. 
Cranston,  and  A.  Fleck  (47,  49,  50). 

To  remove  radium  and  other  radioactive  constituents  from  pitch- 
blende, Hahn  and  Meitner  treated  pulverized  pitchblende  repeatedly 
and  for  long  periods  of  time  with  hot  concentrated  nitric  acid.  From  the 
insoluble  siliceous  residue  they  separated  a  new  radioactive  substance, 
which  they  called  protoactinium.  This  name  has  subsequently  been 
shortened  to  protactinium.  When  they  added  a  little  tantalum  salt  to 
a  solution  containing  protactinium,  the  reactions  of  the  new  substance 
so  closely  resembled  those  of  tantalum  that  Hahn  and  Meitner  were 
unable  to  separate  the  two  substances  (118).  Since  tantalum  is  not 
radioactive,  the  protactinium  could  thus  be  obtained  free  from  other 
radioelements.  Since  protactinium  is  not  an  isotope  of  tantalum,  it 
should  be  possible  to  separate  them  from  each  other  (119).  By  working 
up  large  quantities  of  rich  pitchblende  residues  from  the  Quinine  Works 
at  Braunschweig,  Hahn  and  Meitner  were  able  to  extract  mor.e  active 
preparations  of  the  new  element  (49). 

F.  Soddy  and  J.  A.  Cranston  concluded  in  1918  that  protactinium 
might  possibly  occupy  the  ekatantalum  position  (that  of  element  91  in 
the  periodic  system),  a  view  which  has  since  been  confirmed  (50).  Their 
experiments  were  made  on  pitchblendes  from  India  and  the  Joachimsthal. 

In  1927,  Dr.  Aristid  V.  Grosse*  succeeded  in  preparing  two  milli- 
grams of  a  white  powder  which  was  shown  to  be  the  pentoxide  of  pro- 
tactinium, Pa2O5  (88).  Grosse  and  M.  G.  Agruss  later  worked  up  large 
quantities  of  radium  residues  from  Joachimsthal,  Czechoslovakia,  at 
the  Lindsay  Light  Company.  The  residues  were  extracted  with  hydro- 
chloric acid,  and  the  siliceous  residue  containing  the  protactinium  was 
fused  with  sodium  hydroxide.  After  leaching  the  basic  oxides  from  the 
melt,  Grosse  and  Agruss  precipitated  zirconium  phosphate,  which 

*  The  process  patented  by  Grosse  and  Hahn  for  preparing  pure  Pa2O5  is  described  in 
Chem.  Zentr.,  102,  3525-6  (1931). 


THE  NATURAL  RADIOACTIVE  ELEMENTS 


821 


carried  down  with  it  the  protactinium.  They  succeeded  in  concentrating 
the  protactinium  from  the  original  value  of  about  0.3  gram  per  metric 
ton  in  the  Joachimsthal  residues  to  1  part  per  1000  in  the  plant  product, 
which  they  further  concentrated  in  the  laboratory  by  fractional  crystalli- 
zations of  zirconium  oxychloride  and  repeated  precipitation  of  zirconium 
phosphate.  Most  of  the  zirconium  was  finally  separated  by  sublimation 
of  the  chlorides,  after  which  the  protactinium  was  precipitated  with 
hydrogen  peroxide.  In  this  way  they  isolated  0.1  gram  of  pure  pro- 
tactinium pentoxide  (95). 


Dr.  John  A.  Cranston.  Member  of  the 
Council  of  the  Society  of  Chemical  In- 
dustry. Chairman  of  the  Glasgow  Sec- 
tion. He  collaborated  with  Frederick 
Soddy  in  important  researches  on  radio- 
activity, and  is  an  independent  discov- 
erer of  the  element  protactinium,  Men- 
deleev's predicted  eka-tantalum. 


In  the  fall  of  1934,  Dr.  Grosse  reduced  this  pure  oxide  by  two 
methods  and  obtained  from  it  the  metal  protactinium,  which  is  even  rarer 
than  radium,  but  much  more  permanent  in  air.  In  the  first  method,  he 
bombarded  the  oxide  on  a  copper  target,  in  a  high  vacuum,  with  a  stream 
of  electrons.  After  a  few  hours,  he  obtained  "a  shiny,  partly  sintered, 
metallic  mass,  stable  in  air."  In  his  second  method,  he  converted  the 
oxide  to  the  iodide  (or  chloride  or  bromide)  and  "cracked"  it  in  a  high 
vacuum  on  an  electrically  heated  tungsten  filament,  according  to  the 
reaction: 

2PaI5  =  2Pa  +  5I2 

The  metallic  protactinium  retained  its  bright  luster  for  some  time 
(95). 


822 


DISCOVERY  OF  THE  ELEMENTS 


Proc.  Roy.  Soc.   (London) 


Crystals   o£  Potassium  Protactinium   Fluoride-K2PaF7.      Left:    Dark   field 
illumination;  X  60. 


Dr.  Grosse  then  converted  part  of  his  pure  protactinium  pentoxide 
into  potassium  protactinium  fluoride,  K2PaF7,  which  can  easily  be  dried 
to  constant  weight.  Using  the  classical  method  which  J.-C.  G.  de  Mari- 
gnac  had  used  for  determining  the  atomic  weight  of  tantalum,  he  weighed 
the  new  element  both  as  the  pentoxide  and  as  potassium  protactinium 
fluoride.  His  duplicate  results  for  the  atomic  weight  of  protactinium, 
made  on  this  very  small  sample  but  with  precise  technique  and  apparatus, 
are  230.4  and  230.8.*  These  researches  were  especially  important  be- 
cause they  led  to  a  much  better  understanding  of  the  entire  actinium 
series.  Protactinium  is  an  isotope  of  uranium  Z  and  of  uranium  X2?  and 
thus  there  are  at  least  three  radioactive  elements  all  identical  in  chemical 
and  physical  properties  with  Mendeleev's  predicted  eka-tantalum  (17). 

In  1899  Andre"  Debierne,  a  young  chemist  who  had  served  as  prepa- 
rateur  under  Charles  Friedel  and  who  was  an  intimate  friend  of  the 
Curie  family,  discovered  that  another  radioactive  element  is  carried  down 
with  the  precipitate  of  the  rare  earths  produced  by  adding  ammonium 
hydroxide  to  a  solution  obtained  by  dissolving  pitchblende  (40).  This 
element,  which  he  named  actinium,  was  discovered  independently  in  1902 
by  F.  Giesel,  who  removed  it  with  the  lanthanum  and  cerium  (41)  and 
called  it  emanium. 

In  1949,  about  half  a  century  after  the  discovery  of  actinium,  the 
International  Rare  Metals  Refinery,  Inc.  produced  it  industrially  (134). 
It  is  about  150  times  as  active  as  radium  and  is  a  valuable  source  of  neu- 

*  The  1954  atomic  weight  of  protactinium  is  231. 


THE  NATURAL  RADIOACTIVE  ELEMENTS  823 


Courtesy    Scientific   American 

Apparatus  used  by  Dr.  Aristid  V.  Grosse  in  his  researches  on  protactinium. 
This  diminutive  apparatus  occupies  a  total  length  from  left  to  right  of  about 

eleven  centimeters. 

trons.  Although  actinium  itself  is  a  nearly  pure  beta-ray  emitter, 
actinium  in  equilibrium  with  its  decay  products  is  also  a  powerful  source 
of  alpha-radiation  (134}. 

The  actinium  series  is  very  much  like  that  o£  radium.  In  1904  and 
1905  Giesel  and  T.  Godlewski,  while  working  independently,  discovered 
the  element  actinium  X,  which  is  precipitated  with  the  ferric  hydroxide  by 
adding  an  excess  of  ammonium  carbonate  solution  to  a  solution  con- 
taining actinium  and  iron  (41 9  44). 

Friedrich  O.  Giesel  (born  1852)  was  for  many  years  a  chemist  at 
the  quinine  works  of  Braunschweig  Buchler  and  Company,  and  in  the 
early  days  he  worked  up  large  quantities  of  radioactive  minerals  and 
generously  distributed  his  radium  among  investigators  in  all  parts  of  the 
world  (56). 

Tadeusz  Godlewski,  the  youngest  son  of  Emil  Godlewski,  the  famous 
plant  physiologist,  was  born  on  January  4,  1878,  at  Lemberg,  Poland. 
After  graduating  from  the  ancient  Jagiellonian  University  at  Cracow, 
he  went  to  Stockholm  for  a  year  of  graduate  study  under  Svante  Arrhenius. 
A  year  of  research  under  Sir  Ernest  Rutherford  at  Montreal  resulted  in 
the  publication  of  three  papers  on  radioactivity.  After  returning  to 
Poland,  Godlewski  became  professor  of  physics  and  rector  at  the  Tech- 
nische  Hochschule  of  Lemberg,  where  he  continued  his  original  investiga- 
tion in  radioactivity  and  electrochemistry.  His  life  was  all  too  short, 
and  it  is  believed  that  his  death  in  1921  was  caused  by  leakage  of  coal 
gas  in  his  laboratory  (89). 

In  1906  Professor  Otto  Hahn  discovered  radioactinium  between 
actinium  and  actinium  X  (45).  Actinium  emanation,  or  actinon,  which, 


824 


DISCOVERY  OF  THE  ELEMENTS 


like  radon,  is  an  inert  gas,  was  discovered  independently  by  F.  Giesel  and 
Andre  Debierne  (40,  41}.  The  other  members  of  the  series,  actinium 
A,  B,  C,  C',  C",  and  D,  are  analogous  to  the  corresponding  members  in 
the  radium  series  (43,  64).  It  was  proved  by  B.  B.  Boltwood  that  there 
is  a  genetic  relationship  between  the  uranium,  the  radium,  and  the  ac- 
tinium series  of  elements,  and  in  1915  F.  Soddy  and  Miss  A.  F.  Hitchins 
measured  the  steady  growth  of  radium  in  purified  uranium  preparations 
(39,57). 

THE  THORIUM  SERIES 

The  thorium  series  is  apparently  independent  of  the  three  just  named. 
In  1905  Otto  Hahn,  working  under  Sir  William  Ramsay's  direction,  dis- 
covered radiothorium  in  the  residues  from  a  Ceylon  mineral  called 
thorianite,  and  two  years  later  he  showed  that  mesothorium  is  an  inter- 
mediate disintegration  product  (19,  35,  36). 

Since  the  radioactivity  of  thorium  salts  is  smaller  than  that  of  the 
minerals,  B.  B.  Boltwood  (93)  thought  that  some  of  the  radiothorium 
must  have  been  lost  during  the  purification  process.  On  the  assumption 
that  radiothorium  was  formed  directly  from  thorium,  he  computed  that 
the  half -life  period  of  the  former  ought  to  be  at  least  six  years,  whereas 


Alexander  Smith  Russell.  Scottish 
chemist  who  discovered  the  effect  of  a 
beta-ray  change  on  the  atomic  number 
of  an  element.  Lecturer  on  inorganic 
chemistry  at  Oxford  University.  He 
has  carried  on  chemical  research,  espe- 
cially in  radioactivity,  in  the  laboratories 
of  Soddy  in  Glasgow,  of  Nernst  in  Ber- 
lin, and  of  Rutherford  in  Manchester. 
His  publications  include  many  research 
papers,  literary  contributions,  and  a 
book  on  the  chemistry  of  radioactive 
substances. 


THE  NATURAL  RADIOACTIVE  ELEMENTS 


825 


Halm  obtained  an  experimental  value  o£  only  two  years.  Hahn  there- 
fore assumed  that  there  must  exist  between  thorium  and  radiothorium  an 
unknown  rayless  product,  mesothorium,  which  can  easily  be  separated 
from  thorium  in  the  purification  process. 

He  found  that  freshly  prepared  thorium  salts  have  a  normal  radio- 
activity which  decreases  to  a  minimum  in  4.6  years.  He  computed  that 
the  undiscovered  member  ought  to  have  a  half -life  period  of  five  and 
one-half  years,  and  two  chemists  at  the  University  of  Chicago,  Herbert 
N.  McCoy  (100)  and  William  H.  Ross,  later  verified  this  prediction. 
The  new  element  was  at  first  called  mesothorium.,  but  is  now  known  as 
mesothorium  1  (20,  63),  the  name  having  been  changed  because  Hahn 


Sir  Alexander  Fleck,  1889-  .  Author  of 
many  research  papers  on  the  radioactive 
isotopes.  He  proved  the  inseparability  of 
uranium  Xi  and  radioactinium  from  tho- 
rium, of  thorium  B  and  actinium  B  from 
lead,  of  mesothorium  2  from  actinium,  of 
radium  E  from  bismuth,  and  of  radium  A 
from  polonium,  and  confirmed  the  dis- 
covery of  uranium  X2  by  Fajans  and  O.  H. 
Gb'hring.  Chairman  of  Imperial  Chemi- 
cal Industries,  Ltd.  See  also  ref.  (137). 


afterward  found  that  mesothorium  1  disintegrates  into  a  short-lived  prod- 
uct, mesothorium  2.  Soddy's  brilliant  elucidation  of  the  chemistry  of 
mesothorium  1  led  to  his  theory  of  radioactive  isotopes,  for  which  he  was 
awarded  the  Nobel  Prize  (66). 

Because  of  its  lower  cost,  mesothorium  1  is  frequently  substituted  for 
radium  in  therapy  and  in  the  manufacture  of  luminous  watch-dials.  The 
commercial  process  for  extracting  it  from  the  by-products  of  monazite 
sand  was  long  kept  secret,  but  after  Soddy  and  W.  Marckwald  independ- 
ently discovered  that  it  is  chemically  identical  with  radium,  the  process 
for  extracting  the  latter  element  from  pitchblende  was  adapted  so  that 
it  could  be  used  for  recovering  mesothorium  1  (84,  94) . 


826 


DISCOVERY  OF  THE  ELEMENTS 


In  1902  Rutherford  and  Soddy  added  ammonium  hydroxide  to  a 
thorium  solution,  filtered  off  the  thorium  hydroxide  precipitate,  and  found 
that,  after  they  evaporated  the  thorium-free  filtrate  to  dryness  and  fumed 
off  the  ammonium  salts,  the  residue  was  much  more  active  than  the 
original  thorium  salt  (18).  This  observation  led  them  to  the  discovery  of 
a  new  member  of  the  thorium  series,  which  they  called  thorium  X. 

R.  B.  Owens,  Macdonald  professor  of  electrical  engineering  at  McGill 
University,  and  Sir  Ernest  Rutherford  noticed  that  when  a  thorium  com- 
pound is  placed  in  an  open  vessel  exposed  to  air  currents,  its  radio- 


R.  B.  Owens.  He  observed  in  1899 
that  the  ionization  current  through  a 
confined  volume  of  air  exposed  to  the 
rays  from  thorium  compounds  decreased 
to  a  minimum  when  air  was  drawn 
through  his  apparatus.  Rutherford 
showed  that  this  effect  is  caused  by  the 
emission  of  thorium  emanation,  now 
known  as  thoron.  This  photograph  was 
taken  in  about  1910  when  Professor 
Owens  was  at  McGill  University. 


Photo  by  William  Notman  &  Son,  Ltd. 


activity  is  not  constant,  and  a  study  of  this  anomaly  led  them  to  the 
discovery  that  thorium  gives  off  a  gas,  or  emanation  (21  ,  31),  which  is 
now  known  as  thoron.  It  is  an  isotope  of  radon  and  actinon,  and  was 
the  first  radioactive  gas  to  be  discovered  (20). 

Professor  Hans  Geiger  and  E.  Marsden  noticed  that  the  alpha  par- 
ticles from  thoron  are  expelled  at  such  very  short  intervals  that  they  seem 
to  be  double.  They  found,  as  Rutherford  suggested,  that  this  strange 
behavior  is  caused  by  the  presence  of  a  very  short-lived  decay  product  of 
thoron,  which  they  named  thorium  A  (80).  Prof.  Geiger  was  born  in 


THE  NATURAL  RADIOACTIVE  ELEMENTS 


827 


Frederick  Soddy,  1877-  .  Professor 
of  chemistry  at  Glasgow,  Aberdeen,  and 
Oxford.  Author  of  books  on  radioac- 
tivity  and  economics.  He  showed  that 
when  a  radioactive  element  emits  alpha 
particles,  its  position  in  the  periodic 
table  is  shifted  two  spaces  to  the  left, 
whereas  a  beta-ray  change  causes  a 
shift  of  one  space  toward  the  right. 
This  rule,  which  explains  the  existence 
of  radioactive  isotopes,  was  discovered 
independently  by  A.  S.  Russell,  A.  F. 
Fleck,  F.  Soddy,  and  K.  Fajans. 


Courtesy  Ralph  E.  Oesper 


Neustadt,  Germany,  was  educated  at  Erlangen,  Munich,  and  Manchester, 
and  became  director  of  the  laboratory  for  Radium  Research  at 
Charlottenburg, 

Thorium  A  quickly  decays  into  thorium  B,  another  rather  short-lived 
product,  which  spontaneously  disintegrates,  as  shown  by  Rutherford, 
into  thorium  C  (53).  By  heating  a  lead-encased  platinum  wire  charged 
with  the  mixture  to  700°,  Miss  J.  M.  W.  Slater,  Bathurst  student  at 
Newnham  College,  Cambridge,  succeeded  in  volatizing  the  thorium  B* 
from  the  platinum  and  condensing  it  on  the  cold  lead  cylinder.  At  1000° 
almost  pure  thorium  C  remained  on  the  wire  ( 32 ) . 

It  was  shown  by  E.  Marsden  and  Thomas  Barratt  and  independently 
by  Hahn  and  Meitner  that  thorium  C*  breaks  down  into  thorium  C'  and 
thorium  C"  (20,  34,  76).  The  last  member  of  this  series,  thorium  D,  or 
thorio-lead,  ends  what  Soddy  has  called  "the  stately  procession  of  ele- 
ment evolution"  (57).  Thus  thorium  "disintegrates  in  cascade"  to  form 
the  successive  products:  mesothorium  1,  mesothorium  2,  radiothoriunu 
thorium  X,  thoron,  and  thorium  A,  B?  C,  C'?  C",  and  D. 

The  explanation  of  the  radioactive  isotopes  was  given  independently 
by  Alexander  S.  Russell,  Frederick  Soddy,  and  Kasimir  Fajans  in  1913 
(90).  With  the  aid  of  Alexander  Fleck  at  Glasgow,  who  had  devoted 


*  Before  1911  the  elements  now  known  as  thorium  B  and  thorium  C  were  called, 
respectively,  thorium  A  and  thorium  B. 


828  DISCOVERY  OF  THE  ELEMENTS 

The    Radiooctive     Isotopes      and        thej^      Thansforrna-hons 


Long  arrows  pointing  to  the  left  represent  a-ray  transformations;  short  ones 
pointing  to  the  right  indicate  jS-ray  changes. 

three  years  to  a  thorough  study  of  the  chemical  properties  of  the  radio- 
active elements,  Soddy  deduced  the  following  rule:  The  chemical 
properties  of  an  alpha-ray  product  correspond  with  those  of  an  element 
whose  group  number  in  the  periodic  system  is  -two  less  than  that  of  its 
parent. 

A.  S.  Russell,  Carnegie  Research  Fellow  at  the  University  of  Glas- 
gow, soon  discovered  the  following  corollary  to  this  rule:  The  chemical 
properties  of  a  beta-ray  product  correspond  with  those  of  an  element 
whose  group  number  is  greater  by  one  than  that  of  its  parent. 

That  is,  in  an  alpha-ray  change,  or  expulsion  of  a  helium  atom  with 
double  positive  charge,  the  atomic  number  (serial  number  of  the  element 
in  the  periodic  system)  decreases  by  two,  and  the  atomic  weight  by  four, 
units,  whereas  in  a  beta-ray  transformation  or  emission  of  a  negative 
electron,  the  atomic  number  increases  by  one  unit  while  the  atomic  weight 
remains  unchanged.  Thus  the  combined  effect  of  two  beta-ray  changes 
and  one  alpha-ray  transformation  is  to  produce  an  element  which,  like 
uranium  2,  is  chemically  identical  with  its  great-grandparent.  "Radio- 
active children,"  says  Soddy,  "frequently  resemble  their  great-grand- 
parents with  such  complete  fidelity  that  no  known  means  of  separating 
them  by  chemical  analysis  exists"  (56). 


THE  NATURAL  RADIOACTIVE  ELEMENTS  829 

The  complete  sequence  of  radioactive  changes  in  the  last  twelve 
places  in  the  periodic  system  which  was  worked  out  through  the  researches 
of  A.  S.  Russell,  K.  Fajans,  F.  Soddy,  A.  Fleck,  and  others,  is  given  in  the 
table  reproduced  herewith. 

Thus  it  is  evident  that  there  are  three  natural  radioactive  isotopes 
of  thallium,  seven  of  lead,  four  of  bismuth,  seven  elements  in  the  polonium 
pleiad,  three  inert  radioactive  gases,  four  isotopes  of  radium,  two  of 
actinium,  six  of  thorium,  three  eka-tantalums,  and  three  uraniums. 


The  Curie  Family 


From   "The    Sphere" 


In  1903  M.  and  Mme.  Curie,  together  with  M.  A.-H.  Becquerel,  were 
awarded  the  Nobel  Prize  in  chemistry.  The  Curie  household  with  its  two 
bright  little  daughters  was  a  most  happy  one,  and  the  gifted  parents 
looked  forward  to  a  lifetime  of  united  efforts  for  science.  That  dream  was 
not  to  be  fulfilled.  On  April  19,  1906,  as  Pierre  Curie  was  crossing  a 
busy  street  in  Paris,  he  was  struck  by  a  heavy  vehicle  and  instantly 
killed  (61). 

As  a  result  of  this  frightful  shock,  Mme.  Curie  suffered  a  long,  serious 
illness,  but,  when  she  finally  recovered  she  resolved  to  devote  the  rest  of 
her  life  to  her  children  and  to  science.  She  taught  the  little  girls  herself, 
and  for  a  time  had  charge  of  a  small  private  school  (22}.  The  elder 


830 


DISCOVERY  OF  THE  ELEMENTS 


Mme.  Curie  and  her  daughter,  Mme. 
Joliot-Curie.  The  latter  published 
many  papers  on  the  radioactive  ele- 
ments. During  World  War  I,  while 
still  very  young,  she  assisted  her  mother 
in  the  radiological  service  to  the 
wounded.  With  her  husband,  Dr.  F. 
Joliot  of  the  Institut  de  Radium  in 
Paris,  she  prepared  artificial  radio- 
active elements. 


daughter,  Irene  (Mme.  Joliot),  followed  in  the  footsteps  of  her  illustrious 
parents;  while  Eve,  the  younger  one,  has  become  a  well-known  concert 
pianist  and  has  written  a  splendid  biography  which  intimately  reveals 
the  great  soul  of  Mme.  Curie  (98, 105}. 

Less  than  a  year  after  her  husband's  death,  Mme.  Curie  accepted  a 
professorship  at  the  University  of  Paris.  With  the  able  assistance  of  Pro- 
fessor Andre  Debierne,  who  took  charge  of  the  laboratory  and  taught 
for  many  years  an  ever-increasing  number  of  students  from  all  parts  of 
the  world,  she  directed  the  instruction  and  research  in  radioactivity  (86). 
When  the  university  acquired  new  land,  it  laid  out  a  street  called  the  Rue 
Pierre  Curie  and  built  a  laboratory  for  her.  The  Curie  Institute  and  the 
Pasteur  Institute  work  in  close  harmony,  and  Mme.  Curie  spent  much 
of  her  time  on  researches  dealing  with  the  therapeutic  properties  of 
radium  and  radon  (69).  During  World  War  I  she  had  complete  charge 
of  the  radiological  service  in  French  military  hospitals. 

In  1911  she  was  awarded  the  Nobel  Prize  in  physics,  and  was  thus 
the  only  person  ever  to  have  received  the  Nobel  award  twice.  While 
radium  with  its  dangerous  yet  beneficent  radiations  was  prolonging  count- 
less lives,  it  was  gradually  undermining  the  health  of  its  discoverer,  and 


THE  NATUKAL  RADIOACTIVE  ELEMENTS  831 

on  July  4,  1934,  her  life  of  devotion  to  science  and  humanity  came  to  a 
close  (97). 

Her  years  in  the  adopted  country  had  given  her  a  mode  of  expres- 
sion that  was  truly  French.  She  summarized  her  life  story  in  these  few 
words:  "I  was  born  in  Warsaw  of  a  family  of  teachers.  I  married  Pierre 
Curie  and  had  two  children.  I  have  done  my  work  in  France"  ( 1 ) . 

After  Julius  Elster  and  Hans  Geitel  had  noticed  that  the  electrical 
conductivity  of  the  air  in  caves  and  closed  cellars  is  higher  than  that 
in  the  free  atmosphere,  they  finally  found  that  this  was  caused  by  the 
presence  of  emanations,  or  radioactive  gases,  in  the  ground.  In  a  series 
of  investigations  from  1901  to  1906  they  demonstrated  the  presence  of 
radioactive  elements  in  various  kinds  of  rocks  and  soils,  and  showed 
that  minute  amounts  of  both  radium  and  thorium  are  widely  distributed  in 
the  earth's  crust,  in  spring  waters,  in  sea  water,  and  in  the  atmosphere 

(85,  96). 

J.  J.  Thomson,  A.  Sella,  and  I.  Pochettino  discovered  independently 
in  1902  that  certain  natural  waters  are  radioactive  (64).  The  activity 
of  most  radioactive  springs  is  due  not  to  radium  itself  but  to  its  disintegra- 
tion product,  radon,  which  the  water  has  dissolved  while  flowing  through 
rocks  containing  radium  (116). 

Radium  is  occasionally  present  in  bone  and  teeth  (117). 

ARTIFICIAL  RADIOACTIVITY* 

The  creation,  by  neutron  bombardment  of  uranium,  of  the  so-called 
"transuraniums"  is  based  on  the  discovery  of  artificial  radioactivity  by 
M.  and  Mme.  Joliot-Curie.  Irene  Curie  was  born  in  Paris  in  September, 
1897,  the  elder  daughter  of  M,  and  Mme.  Pierre  Curie  of  honored  memory. 
Both  in  Poland  and  in  France  she  had  many  relatives  who  were  devoting 
their  lives  to  science,  and  from  her  earliest  childhood  she  lived  in  a 
scientific  atmosphere,  among  distinguished  chemists  and  physicists.  When 
Ir&ne  was  less  than  a  year  old,  her  mother  discovered  the  radioactive 
element  polonium,  which  was  destined  to  play  an  important  part  in  the 
later  researches  of  both  mother  and  daughter.  A  few  months  later  M. 
and  Mme.  Curie  discovered  another  element  of  even  greater  importance, 
which  they  named  radium. 

While  they  were  patiently  carrying  out  the  laborious  but  brilliantly 
executed  investigations  on  which  the  science  of  radioactivity  is  based, 
Irene  was  left  under  the  affectionate  care  of  her  grandfather,  Dr.  Eugene 
Curie,  a  cultured  physician,  well  versed  in  the  sciences.  When  she  was 
seven'years  old,  her  parents,  together  with  Henri  Becquerel,  were  awarded 

*  The  section  on  artificial  radioactivity  was  first  published  in  April,  1936,  for  the 
Kansas  City  Meeting  of  the  American  Chemical  Society. 


832 


DISCOVERY  OF  THE  ELEMENTS 


Mme.  Joliot-Curie,*  1897-1956.  Daugh- 
ter of  Pierre  and  Marie  Curie.  She  made 
many  original  contributions  to  radioac- 
tivity and  collaborated  with  her  husband 
and  her  mother  in  many  brilliant  re- 
searches. M.  and  Mme.  Joliot  and  J. 
Chadwick  showed  that  when  light  ele- 
ments like  beryllium  or  boron  are  bom- 
barded with  swift  a-particles,  a  highly 
penetrating  stream  of  uncharged  par- 
ticles or  neutrons,  is  emitted.  Each 
neutron  is  believed  to  consist  of  one 
positive  proton  and  one  negative  elec- 
tron closely  bound  together. 


the  Nobel  Prize  in  physics.  Mme.  Curie  once  said,  "As  our  elder  daughter 
grew  up,  she  began  to  be  a  little  companion  to  her  father,  who  took  a  livery 
interest  in  her  education  and  gladly  went  for  walks  with  her  in  his  free 
times,  especially  on  his  vacation  days.  He  carried  on  serious  conver- 
sations with  her,  replying  to  all  her  questions  and  delighting  in  the  pro- 
gressive development  of  her  young  mind"  (120).  When  Irene  Curie  was 
only  eight  years  old,  however,  she  suffered  the  cruel  loss  of  her  affec- 
tionate father,  who  was  killed  in  a  traffic  accident. 

She  received  her  earliest  instruction  from  two  Polish  governesses, 
one  of  them  a  cousin  of  Mme.  Curie.  Thus  she  soon  learned  to  under- 
stand and  love  the  language  and  culture  of  her  mother's  native  country. 
After  studying  for  a  time  in  a  private  school  in  Paris,  she  attended  for 
two  years  a  cooperative  school  in  which  Mme.  Curie  and  other  members 
of  the  university  staff  united  to  give  their  own  children  the  advantages  of 
a  well-balanced  literary,  artistic,  scientific,  and  physical  education  in 
which  practical  experiments  played  a  large  part.  According  to  Mme. 
Curie,  Irene  "resembled  her  father  in  the  form  of  her  intelligence.  She 
was  not  quick,  but  one  could  already  see  that  she  had  a  gift  of  reasoning 
power  and  that  she  would  like  science."  As  a  girl  of  fourteen,  Irene  went 
to  Stockholm  to  witness  the  solemn,  inspiring  ceremony  in  which  her 

*  Courtesy  M.  Freymann,  Hermann  et  Cie.,  Paris. 


THE  NATURAL  RADIOACTIVE  ELEMENTS  833 

mother  was  awarded  the  Nobel  Prize  in  chemistry.  Mile.  Curie  later 
attended  a  Paris  college,  passed  her  bachelor's  examination  at  an  un- 
usually early  age,  and  continued  her  scientific  studies  at  the  Sorbonne. 

During  and  after  the  World  War,  Mme.  Curie  established  many 
radiological  stations  and  radiologic  motor  cars,  with  which  she  taught 
volunteer  helpers  how  to  use  Rontgen-ray  equipment  in  the  examination 
of  the  wounded.  This  made  it  possible  to  determine  the  exact  location 
of  projectiles  and  to  save  many  men  from  death  or  permanent  disability, 
On  several  of  her  trips  to  the  ambulance  stations  in  the  war  zone,  Mme. 
Curie  was  accompanied  by  Irene,  who  was  then  only  seventeen  years  old. 
Although  she  was  just  beginning  her  advanced  studies  at  the  Sorbonne, 
Mile.  Curie,  eager  to  be  of  service,  studied  nursing  and  radiology,  and 
did  ambulance  work  at  the  front,  for  which,  at  the  close  of  the  war,  she 
was  awarded  a  medal.  In  1916  a  department  of  radiology  was  added  to 
the  Nurses'  School,  where,  according  to  Mme.  Curie,  "a  few  persons  of 
good  will,  among  them  my  daughter"  trained  one  hundred  and  fifty 
operators.  Throughout  the  entire  duration  of  the  war,  Mme.  Curie  took 
almost  no  vacation.  "My  older  daughter,"  said  she,  "would  scarcely  take 
any,  and  I  was  obliged  to  send  her  away  sometimes  to  preserve  her  health. 
She  was  continuing  her  studies  in  the  Sorbonne,  and  .  .  .  was  helping  me 
with  my  war  work." 

In  1921  Mme.  Curie  visited  the  United  States,  where  she  received 
many  honors,  including  the  gift  of  a  gram  of  radium  from  the  women  of 
America.  Irene  and  her  younger  sister,  £ve-Denise,  accompanied  their 
mother  on  this  visit. 

In  the  same  year  Mile.  Curie  published  in  the  Comptes  rendus  her 
first  scientific  paper,  which  was  entitled  "The  atomic  weight  of  the 
chlorine  in  certain  minerals."  Upon  examining  three  chlorine  minerals 
( a  Canadian  sodalite,  a  Norwegian  chlor-apatite,  and  a  sample  of  sodium 
chloride  from  a  Central  African  desert,  which  had  probably  been  formed 
by  the  weathering  of  local  Archaean  granites),  she  found  the  chlorine 
in  the  first  two  to  be  identical  within  the  experimental  error  of  0.02  atomic 
weight  unit  with  that  in  an  ordinary  chloride.  "The  results  concerning 
the  sodalite  and  the  apatite  lead  one  to  think,"  said  she,  "that  in  general 
the  atomic  weight  of  the  chlorine  contained  in  ancient  minerals  scarcely 
differs  from  that  of  normal  chlorine  from  sea  water;  if  this  result  were 
generalized,  one  would  be  led  to  conclude  that  there  was  a  very  perfect 
mingling  of  the  two  isotopes  before  the  formation  of  the  mineral  or 
rather  that  the  two  isotopes  were  formed  from  the  beginning  in  a  practi- 
cally constant  proportion."  The  chlorine  in  the  sodium  chloride  from 
the  African  desert  apparently  had  a  higher  atomic  weight,  however,  for 
Mile.  Curie  obtained  35.60  for  its  atomic  weight,  even  though  bromine 
and  iodine  were  absent  ( 121 ) . 


834  DISCOVERY  OF  THE  ELEMENTS 

Beginning  in  1922  she  published  a  long  series  of  excellent  researches 
on  polonium,  in  which  she  determined  the  velocity  of  its  alpha-rays  and 
the  distribution  of  their  lengths,  and  observed  their  ionizing  power,  the 
oscillations  in  their  paths,  and  the  homogeneity  of  their  initial  velocity. 
In  1923  she  used  an  original  method  to  determine  the  range  in  air  of 
its  alpha-particles. 

In  the  following  year  Miles.  Curie  and  C.  Chamie  measured  the  half- 
life  period  of  radon  by  a  method  which  is  very  simple  in  principle.  If 
a  single  tube  of  radon  placed  in  the  ionization  chamber  yields  at  time  t  a 


Jean-Fr<§de"ric  Joliot,*  1900-1958.  Phy- 
sicist and  chemist  at  the  Curie  Institute. 
He  has  made  many  important  researches 
on  the  phenomenon  of  recoil  and  the 
conservation  of  momentum,  on  the  elec- 
trochemical behavior  of  the  radioele- 
ments,  and  on  the  expulsion  of  atomic 
nuclei  and  the  existence  of  the  neutron. 


given  current  i,  and  the  time  ?  is  noted  at  which  the  same  current  i  is 
obtained  with  two  tubes  of  radon  (the  second  of  which  is  exactly  equiva- 
lent to  the  first),  then  *  —  if  =  T9  the  half -life  period  of  radon.  Since 
it  is  impossible  to  prepare  two  tubes  of  radon  of  exactly  the  same  activity, 
Miles.  Curie  and  Chamie  applied  a  correction.  Their  value  for  this  con- 
stant was  3.823  days  (122). 

Mile.  Curie's  doctor's  dissertation  in  1925  was  entitled  "Investigation 
regarding  the  alpha  rays  of  polonium."  With  the  help  of  various  collabo- 
rators, including  F.  Behounek,  Mile.  Chamie,  J.  d'Espine,  G.  Fournier, 

*  Courtesy  M,  Freymann,  Hermann  et  Cie., 


THE  NATURAL  RADIOACTIVE  ELEMENTS  835 

N.  Yamada,  and  P.  Mercier,  she  published  a  number  of  researches  on 
other  radioactive  elements,  including  radium  C,  radium  C',  radon, 
radium  A,  and  radium  E. 

In  1926  Mile.  Curie  married  M.  Frederic  Joliot,  a  young  scientist 
whose  tastes,  interests,  and  intellectual  attainments  were  entirely  com- 
parable to  her  own.  He  was  born  in  Paris  in  1900.  In  1923  he  com- 
pleted the  engineering  course  at  the  Ecole  de  Physique  et  de  Chimie  In- 
dustrielle.  Upon  the  recommendation  of  his  professor,  M.  Paul  Langevin, 
he  became  preparateur  under  Mme.  Curie  and  continued  his  studies  at 
the  Sorbonne.  He  succeeded  M.  Andre  Debierne  as  lecturer  at  the  Faculty 
of  Sciences.  So  intimate  was  the  collaboration  between  M.  and  Mme. 
Joliot  that,  when  a  new  discovery  was  made,  they  themselves  scarcely 
knew  in  which  mind  the  original  concept  first  arose.  In  order  that  the 
honored  name  Curie  might  be  handed  down  to  their  children  and  pos- 
terity, M.  Joliot  gladly  consented,  at  the  time  of  his  marriage,  to  add  this 
name  to  his  own.  Thus  they  were  known  either  as  M.  and  Mme.  Joliot- 
Curie  or  simply  as  M.  and  Mme.  Joliot. 

Their  joint  papers  on  "The  numbers  of  ions  produced  by  alpha 
rays  of  radium  C'  in  air"  were  published  in  the  Comptes  rendus  in  1928. 
In  the  following  year  they  investigated  the  nature  of  the  absorbable 
radiation  which  accompanies  the  alpha-rays  from  polonium.  In  1930  M. 
Joliot  presented  his  thesis  for  the  doctorate,  which  was  entitled  "The 
electrochemistry  of  the  radio-elements/'  and  Mme.  Joliot  continued  her 
study  of  polonium  ( 123 ) . 

In  speaking  of  the  spontaneous  disintegration  of  the  natural  radio- 
elements,  Mme.  Curie  pointed  out  in  her  fine  biography  of  her  husband 
that  "In  many  cases,  up  to  the  present,  no  exterior  action  has  shown 
itself  effective  in  influencing  this  transformation."  This  view  remains  un- 
shaken even  to  the  present  day.  Near  the  very  close  of  her  life,  however, 
Mme.  Curie  witnessed  the  discovery  by  her  own  daugher  and  son-in-law 
of  a  wonderful  new  type  of  radioactivity,  artificially  produced  (124).  The 
transformation  of  one  element  into  another  stable,  inactive  one  had 
already  been  accomplished.  Lord  Rutherford,  in  1919,  had  bombarded 
nitrogen  with  swift  alpha-particles,  or  helions,  and  liberated  high-speed 
protons,  and  P.  M.  S.  Blackett  had  shown  that  the  nitrogen  nucleus  had 
captured  the  alpha-particle  and  that  the  resulting  element  was  an  iso- 
tope of  oxygen.  The  nuclear  reaction  was  therefore  as  follows: 

7N14  +  2He4  =  8O1T  +  iH1 

helion  proton 

Artificial  transmutations  into  other  stable  elements  had  also  been  accom- 
plished. 

In  1930  W.  Bothe  and  H.  Becker  observed  a  very  penetrating  radia- 


836  DISCOVERY  OF  THE  ELEMENTS 

tion  from  beryllium  which  had  been  bombarded  with  helions.  M.  and 
Mme.  Joliot-Curie  found  that  when  they  placed  paraffin  or  other  hydro- 
gen-containing substances  before  the  window  of  an  ionization  chamber, 
the  ionization  produced  by  these  new  rays  increased;  for  the  protons 
which  were  ejected  from  the  paraffin  by  the  radiation  from  the  beryllium 
had  a  higher  ionizing  power  than  the  beryllium-radiation  itself  (125). 
Professor  James  Chadwick  proved  that  the  activity  of  the  beryllium  is 
not  merely  a  hard  gamma-radiation,  as  at  first  supposed,  but  that  neutrons, 
or  uncharged  particles  of  mass  one,  are  also  ejected.  Each  neutron  con- 
sists of  one  proton  and  one  negative  electron,  or  negatron,  closely  bound 
together;  hence  its  atomic  number  is  zero.  The  nuclear  reaction  for  the 
change  which  occurs  when  beryllium  is  bombarded  with  helions  is  as 
follows : 

4Be9  -f  2He4  =  6C12  +  Onl  +  gamma  rays 

neutron 

M.  and  Mme.  Joliot  showed  that  boron  and  lithium,  when  they  are  bom- 
barded with  alpha-rays  from  polonium,  also  emit  penetrating  radiations 
( 126 ) .  Their  work  gave  early  evidence  of  the  probable  existence  of  the 
neutron,  a  hypothesis  which  has  since  been  fully  verified  by  the  researches 
of  Professor  James  Chadwick,  the  1935  Nobel  laureate  in  physics  (127). 

Early  in  1934,  M.  and  Mme.  Joliot-Curie  observed  that  in  some  kinds 
of  transmutation,  true  radio-elements  are  produced  which,  after  their  artifi- 
cial creation,  continue  for  a  measurable  period  of  time  to  emit  positive  or 
negative  electrons  as  they  disintegrate  at  last  into  stable  elements  ( 128 ) . 
When  M.  and  Mme.  Joliot  bombarded  boron,  aluminum,  or  magnesium 
with  helions  from  polonium  and  photographed  the  fog-tracks  which  the 
ejected  electrons  made  in  a  Wilson  expansion  chamber,  they  noted  that, 
even  after  the  removal  of  the  alpha-ray  source,  an  activity  remained  which, 
like  that  of  the  natural  radioactive  elements,  decreased  in  geometrical 
proportion  with  the  time.  The  radiations  from  the  bombarded  boron  and 
aluminum  consisted  of  positrons;  irradiated  magnesium,  however,  gave 
off  a  radiation  consisting  of  both  positrons  and  negatrons. 

Since  the  alpha-ray  impacts  shattered  only  a  minute  proportion  of  the 
total  number  of  atoms  of  boron,  aluminum,  or  magnesium,  the  chemical 
identification  of  the  products  was  extremely  difficult.  These  indefatigable 
workers,  however,  accomplished  even  this.  Although  it  would  have 
been  impossible  to  identify  the  products  simply  by  ordinary  chemical 
means,  the  Joliots  were  able  to  take  advantage  of  the  radioactive  nature 
of  the  products  formed.  Since  they  had  good  reason  to  believe  that  the 
boron  atom  had  captured  a  helion  and  ejected  a  neutron  and  that  the  new 
element  was  therefore  probably  an  isotope  of  nitrogen,  they  heated  some 
bombarded  boron  nitride  with  caustic  soda  and  found  that  the  liberated 


THE  NATURAL  RADIOACTIVE  ELEMENTS  837 

ammonia  carried  with  it  the  new  activity,  leaving  the  residual  boron 
inactive.  The  nuclear  reaction  which  occurred  during  the  alpha-ray  bom- 
bardment was  therefore  as  follows: 


The  new  product,  which  they  named  radionitrogen,  was  a  hitherto 
unknown  radioactive  isotope  of  ordinary  nitrogen.  It  disintegrates  with  a 
half  period  of  fourteen  minutes  and  expulsion  of  positrons,  forming  a 
stable,  inactive  isotope  of  carbon: 

7N13  =  6C13  +  i«° 

positron 

Since  the  Joliot-Curies  believed  that  a  similar  capture  of  the  alpha- 
particle,  with  formation  of  an  isotope  of  phosphorus,  had  occurred  during 
the  bombardment  of  the  aluminum,  they  treated  a  piece  of  irradiated 
aluminum  with  hydrochloric  acid.  The  liberated  hydrogen  carried  with  it 
the  new  activity,  probably  in  the  form  of  phosphine,  leaving  the  aluminum 
residue  inactive.  The  nuclear  reaction  which  took  place  during  the  bom- 
bardment was  therefore  as  follows: 

isAF  +  2He4  =  15P30  +•  on1 

The  radio-phosphorus,  a  hitherto  unknown  isotope  of  ordinary  phosphorus, 
disintegrates  with  a  half  period  of  three  minutes  and  fifteen  seconds,  ac- 
cording to  the  following  reaction: 

i5P30  =  wSi80  +  ie° 

M.  and  Mme.  Joliot-Curie  showed  that  the  magnesium  atom,  when 
similarly  bombarded,  also  captures  a  helion  and  emits  a  neutron,  as 
follows: 

12Mg24  +  2He4  =  i4Si27  +  on1 

The  resulting  radio-silicon  decays  with  a  half-life  period  of  two  minutes 
and  forty-five  seconds,  emitting  both  positrons  and  negatrons. 

Since  other  projectiles,  such  as  neutrons,  protons,  and  deuterons, 
have  also  been  used  to  produce  artificial  radioactivity,  the  number  of 
active  elements  thus  created  already  exceeds  by  far  the  number  of 
naturally  occurring  radio-elements  (129,  130,  131).  By  January,  1940, 
three  hundred  and  thirty  artificial  radioactivities  had  been  described;  these 
include  isotopes  *of  every  known  element  in  the  range  of  atomic  numbers 
1  to  85  inclusive,  as  well  as  isotopes  of  thorium  (atomic  number  90)  and 
of  uranium  (atomic  number  92)  (132).  Thus  the  work  of  M.  and  Mme. 
Joliot-Curie  opened  up  vast  avenues  of  research  on  the  physical,  chemical, 
and  radioactive  properties  of  these  isotopes  and  on  their  therapeutic 
uses.  In  1935  they  were  awarded  the  Nobel  Prize  in  chemistry  (133). 


838  DISCOVERY  OF  THE  ELEMENTS 

M.  and  Mme.  Joliot-Curie  made  further  studies  on  the  gamma- 
radiation  of  ionium,  on  chain  reactions,  and  on  neutrons  and  artificial 
radioactivity.  The  elements  discovered  with  the  aid  of  this  new  science 
will  be  discussed  in  Part  31.  Mme.  Joliot  Curie  died  in  Paris  on  March 
17, 1956  (136)  after  distinguished  service  to  France.  Frederic  Joliot-Curie 
died  in  Paris  on  August  14, 1958. 


LITERATURE  CITED 

( 1 )  CURIE,  MME.,  "Pierre  Curie,"  English  translation  by  Charlotte  and  Vernon 

Kellogg,  The  MacmiUan  Co.,  New  York  City,  1926,  pp.  24-6. 

(2)  RAMSAY,  SIR  WM.?  "The  death-knell  of  the  atom,"  Ind.  Eng.  Chem.,  News 

Ed.,  8,  18  (Jan.  20,  1930).    Poem  written  in  1905. 

(3)  CURIE,  MME.,  "Pierre  Curie,"  ref.  (I),  pp.  54-72. 

(4)  HARROW,  B.,  "Eminent  Chemists  of  Our  Time,"  D.  Van  Nostrand,  Inc.,  New 

York  City,  1920,  p.  158. 

(5)  "Editor's  outlook.    Marie  Sklodowska  Curie,"  J.  Chem.  Educ.,  7,  225-7  (Feb., 

1930). 

(6)  MARCKWALD,  W.,  "Die  Radioaktivitat,"  Ber.,  41,  1524-61  (May,  1908).    A 

review. 

(7)  MENDELEEV,  D.,  "Principles  of  Chemistry,"  Vol.  2,  English  translation  from 

5th  Russian  edition,  Longmans,  Green  and  Co.,  London,  1891,  p.  447,  foot- 
note. 

(8)  CURIE,  MME.,  "Pierre  Curie,"  ref.  (1),  pp.  133  and  186-7. 

(9)  JONES,  HARRY  C.,  "The  Electrical  Nature  of  Matter  and  Radioactivity/'  D. 

Van  Nostrand  Co.,  Inc.,  New  York  City,  1906,  p.  56. 
(JO)     OSTWALD,  W.,  "Lebenslinien,  eine  Selbstbiographie,"  Vol.  3,  Klasing  &  Co., 

Berlin,  1927,  p.  158. 
(12)     FARBER,   E.,    "Geschichtliche  Entwicklung   der   Chemie,"   Springer,    Berlin, 

1921,  p.  279. 

(12)  HAHN,  O.,  "tfber  eine  neue  radioaktive  Substanz  im  Uran,"  Ber.,  54,  1131-42 

(June  11,  1921);  "tft>er  das  Uran  Z  und  seine  Muttersubstanz,"  Z.  physik. 
Chem.,  103,  461-80  (Hefte  5  and  6,  1923). 

(13)  "Editor's  outlook.     Bertram  Borden  Boltwood,"  J.  Chem.  Educ.,  6,  602-4 

(Apr,  1929). 

(14)  HEVESY,  G.  and  F.  PANETH,  "A  Manual  of  Radioactivity,"  English  translation 

by  Lawson,  Oxford  University  Press,  London,  1926,  p.  225. 

(15)  RUTHERFORD,   E.,   "Radioactive   Transformations,"   Charles   Scribner's   Sons, 

New  York  City,  1906,  p.  70. 

(16)  HARROW,  B.,  "Eminent  Chemists  of  Our  Time,"  ref.  (4),  pp.  73-5. 

(17)  GROSSE,  A.  V.,  "The  analytical  chemistry  of  element  91,  ekatantalum,  and  its 

difference  from  tantalum,"  /.  Am.  Chem.  Soc.,  52,  1742-7  ( May,  1930). 

(18)  RUTHERFORD,  E.  and  F.  SODDY,  "The  radioactivity  of  thorium  compounds.    I. 

An  investigation  of  the  radioactive  emanation,"  Trans.  Chem.  Soc.,   81, 
321-50;  "II.    The  cause  and  nature  of  radioactivity,"  ibid.,  837-60  ( 1902). 

(19)  HAHN,  O.,  "ttber  ein  neues  die  Emanation  des  Thoriums  g^bendes  radioaktives 

Element,"  Jahrb.  der  Radioaktivitat,  2,  233-66  (Heft  3,  1905);  Proc.  Roy. 
Soc.  (London),  76A,  115-17  (Mar.  7,  1905). 

(20)  MELLOR,  J.  W.,  "Comprehensive  Treatise  on  Inorganic  and  Theoretical  Chem- 

istry," Vol.  7,  Longmans,  Green  and  Co.,  New  York  City,  1927,  pp.  184- 
203.    Article  on  the  "Raolioactivity  of  thorium." 

(21 )  JONES,  H.  C.,  "Electrical  Nature  of  Matter  and  Radioactivity,"  ref.  (9),  p.  111. 

(22)  CURIE,  MME.,  "Pierre  Curie,"  ref.  (1 ),  pp.  195-6. 


THE  NATURAL  RADIOACTIVE  ELEMENTS  839 

(23)  DOLT,  M.  L.,  "Chemical  French/'  Chemical  Publishing  Co.,  Easton,  Pa.,  1918, 

pp.  282-312.  Article  by  MME.  CURIE,  "Recherches  sur  les  substances  radio- 
actives/' 

(24)  CURIE,  MME.,  "Recherches  sur  les  substances  radioactives,"  Ann.  chim.  phys., 

[7],  30,  99-203  (Oct.,  1903). 

(25)  SCHMIDT,  G.  C.,  Wied.  Ann.,  65,  141  (1898). 

(26)  CURIE,  MME.,  "Rayons  emis  par  les  composes  de  ruranium  et  du  thorium/* 

Compt.  rend.,  126,  1101-3  (Apr.  12,  1898). 

(27)  CURIE,  P.  and  MME.  CURIE,  "Sur  une  substance  nouvelle  radioactive,  contenue 

dans  la  pechblende,"  Compt.  rend.,  127,  175-8  (July  18,  1898). 

(28)  CURIE,  P.  and  MME.  CURIE,  "Sur  une  nouvelle  substance  fortement  radio- 

active contenue  dans  la  pechblende,"  ibid.,  127,  1215-7  (Dec.  26,  1898). 

( 29 )  MARCKWALD,  W.,  "Ueber  den  radioactiven  Bestandtheil  des  Wismuths  aus  Joa- 

chimsthaler  Pechblende/'  Ber.,  35,  2285-8;  4239-41  (1902);  36,  2662-7 
(1903);  "Ueber  das  Radiotellur,"  38,  591-4  (1905). 

(30)  CROOKES,  W.,  "Radioactivity  of  uranium,"  Chem.  News,  81,  253-5  (June  1, 

1900);  265-7  (June  8,  1900);  Proc.  Roy.  Soc.  (London),  66,  409  (May  10, 
1900). 

(31)  OWENS,  R.  B.,  "Thorium  radiation,"  Phil  Mag.,  [5],  48,  360-87  (Oct.  1899); 

E.  RUTHERFORD,  "A  radioactive  substance  emitted  from  thorium  com- 
pounds/' 49,  1-14  (Jan.,  1900);  "Radioactivity  produced  in  substances  by 
the  action  of  thorium  compounds,"  ibid.,  161-92  (Feb.,  1900);  E.  RUTHER- 
FORD and  F.  SODDY,  "An  investigation  of  the  radioactive  emanation  pro- 
duced by  thorium  compounds,"  ibid.,  [6],  4,  569  (Jan.  16,  1902);  Chem. 
News,  85,  55-6  (Jan.  31,  1902);  261-2  (May  30,  1902);  271-2  (June  6, 
1902);  282-5  (June  13,  1902);  293-5  (June  20,  1902);  304-8  (June  27, 
1902). 

(32)  SLATER,  J.  M.  W.,  "On  the  excited  activity  of  thorium,"  Phil  Mag.,  [6],  9, 

628-44  (May,  1905);  Chem.  Zentr.,  76  [1],  1629  (June  21,  1905). 

(33)  FAJANS,  K.,  "Ueber  die  komplexe  Natur  von  Radium  C/'  Physik.  Z.,  12,  369- 

77  (May  15,  1911);  "Ueber  die  Verzweigung  der  Radiumzerfallsreihe," 
ibid.,  13,  699-705  (Aug.  1,  1912);  "Das  Verzweigungsverhaltnis  und  das 
Atomgewicht  der  Ct-Glieder  der  drei  radioaktiven  Umwandlungsreihen," 
Physik.  Z.,  14,  951-3  (Oct.  1,  1913). 

(34)  HAHN,  O.,  "Ueber  einige  Eigenschaften  der  a-Strahlen  des  Radiothoriurns," 

Physik.  Z.,  7,  412-19,  456-62  (1906). 

(35)  HAHN,   O.,   "A  new  radioactive  element  which  emits  thorium   emanation," 

Chem.  News,  92,  251-2  (Dec.  1,  1905). 

(36)  HAHN,    O.,   "Ein   neues   Zwischenprodukt  im   Thorium,"    Ber.,   40,    1462-9 

(1907);  "Ueber  die  Strahlung  der  Thorium-produkte,"  ibid.,  330^-8 
(1907). 

(37)  DORN,  F.  E.,  "Von  radioactiven  Substanzen  ausgesandte  Emanation/'  Abh. 

Naturf.  Ges.,  Halle,   1900. 

(38)  HOFMANN,  K.  A.  and  E.  STRAUSS,  "Radioactives  Blei  und  radioactive  seltene 

Erden,"  Ber.,  33,  3126-31  (1900);  34,  8-11,  907-13  (1901);  3033-9 
(1901). 

(39)  BOLTWOOD,  B.  B.,  "The  production  of  radium  from  uranium/*  Am.  J.  Sci.,  [4], 

20,  239-44  (No.  117,  1905);  "Note  on  a  new  radioactive  element,"  ibid., 
24,  370-2  (No.  142,  1907);  "On  the  ultimate  disintegration  products  of  the 
radioactive  elements,"  ibid.,  20,  253-67  (No.  118,  1905). 

(40)  DEBIERNE,  A.,  "Sur  une  nouvelle  matiere  radioactive/'  Compt.  rend.,  129, 

593-5  (Oct.  16,  1899);  "Sur  un  nouvel  element  radioactif:  ractiimim," 
130,  906-8  (Apr.  2,  1900);  "Sur  du  baryum  radioactif  artificiel,"  131,  333- 
5  (July  30,  1900);  136,  446-9  (Feb.  16,  1903);  671-3  (Mar.  16,  1903); 
"Sur  Temanation  de  Tactinium/'  138,  411-14  (Feb.  15,  1904);  "Sur  Tactin- 
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141,383-5  (Aug.  14,  1905). 


840  DISCOVERY  OF  THE  ELEMENTS 

(41}     GIESEL    F.  O.,  "Ueber  Radium  und  radioactive  Stoffe,"  Ber.,  35,  3608-11 
(1902);  "Ueber  den  Emanationskorper  aus  Pechblende  und  uber  Radium 
ibid    36  342-7  (1903);  "Ueber  den  Emanationskorper  (Emaniirm),    ibid., 
37,  169^-9,  3963-6  (1904);  38,  775-8  (1905);  40,  3011-15  (1907) 

(42)  HONIGSCHMID,  O.,  "Ueber  Radioelemente,"  Ber.,  49,  1835-65    (1917).     A 

(43)  BROOKsT'H.,  "A  volatile  product  from  radium,"  Nature,  70,  270   (July  21, 

1904);  Phil.  Mag.,  [6],  8,  373  (Sept.,  1904).  ?> 

(44)  GODLEWSKI,  T.,  "A  new  radioactive  product  from  actinium,    Nature,  71,  294- 

5  (Jan.  26,  1905);  "Actinium  and  its  successive  products,"  Phil.  Mag.,  [6], 

(45)  HAHN,  O.,  "Ueber  em  neues  Produkt  des  Actiniums,"  Ber.,  39,  1605-7  ( 1906). 

(46)  HAHN,  O.  and  L.  MEITNER,  "Ueber  das  Uran  Y,"  Physik.  Z.,  15,  236-40 

(Mar.  1,  1914).  . 

(47)  HAHN,  O.  and  L.  MEITNER,  "Ueber  die  Eigenschaften  des  Protoaktmiums, 

Ber.,  54,  69-77  (1921). 

(48)  FAJANS,  K.  and  O.  H.  GOHRING,  "Ueber  das  Uran  X2-das  netie  Element  der 

Uranreihe,"  Physik.  Z.,  14,  877-84  (Sept.  15,  1913);  Naturwissenschaften, 
1,339(1913).  .  . 

(49)  HAHN,  O.  and  L.  MEITNER,  "Die  Muttersubstanz^des  Actiniums,  em  neues 

radioaktives  Element  von  langer  Lebensdauer,"   Physik.   Z.,    19,   208-18 
(May  15,  1918);  Naturwissenschaften,  6,  324  (1918). 

(50)  SODDY,  F.  and  J.  A.  CRANSTON,  "The  parent  of  actinium,"  Nature,  100,  498-9 

(Feb.  21,  1918);  Proc.  Roy.  Soc.  (London),  94A,  384  (Feb.  7,  1918). 

(51)  BECQUEREL,  A.-H.,  "Note  sur  quelques  proprietes  du  rayonnement  de  1'ura- 

nium  et  des  corps  radioactifs,"  Compt.  rend.,  128,  771-7  (Mar.  27,  1899). 

(52)  DEMARCAY,  E.-A.,  "Sur  le  spectre  d'une  substance  radioactive,"  Compt.  rend., 

127,  1218  (Dec.  26,  1898). 

(53)  RUTHERFORD,  E.,  "The  succession  of  changes  in  radioactive  bodies,"  Phil. 

Mag.,  8,  636   (1904);  Phil.  Trans.,  204A,  169-219   (1904);  "Slow  trans- 
formation products  of  radium,"  Nature,  71,  341-3  (Feb.  9,  1905). 

(54)  "Classics  of  science:     radioactive  substances,"  Sci.  News  Letter,  14,  137—8 

(Sept.  1,  1928). 

(55)  CURIE,  MME.,  "Recherches  sur  les  Substances  Radioactives,     2nd  ed.,  Gau- 

thier-Villars,  Paris,  1904,  155  pp.    Thesis. 

(56)  SODDY,  F.,  "The  Interpretation  of  Radium,"  4th  ed.,  G.  P.  Putnam's  Sons, 

New  York  City,  1922,  260  pp. 

(57)  Ibid.,  p.  134. 

(58)  LODGE,   "Becquerel  memorial   lecture,"   Trans.    Chem.    Soc.,    101,    2005-42 

(1912). 

(59)  ANTONOFF,  G.  N.,  "The  disintegration  products  of  uranium,"  Phil.  Mag.,  [6], 

22,  419-32  (Sept.,  1911);  "On  the  existence  of  uranium  Y,"  ibid.,  26,  1058 
(Dec.,  1913). 

(60)  DANNE,  J.,  "Les  sels  de  radium,"  La  Nature,  32,  [1],  214-18  (Mar.  5,  1904), 

243-6  (Mar.  19,  1904). 

(61)  F,  S.,  "Professor  Pierre  Curie,"  Nature,  73,  612-13  (Apr.  26,  1906). 

(62)  RAMSAY,  W.,  "Radium  emanation,"  Nature,  76,  269  (July  18,  1907). 

(63)  McCoY,  H.  N.  and  W.  H.  Ross,  "The  specific  radioactivity  of  thorium  and 

the  variation  of  the  activity  with  chemical  treatment  and  with  time,"  /.  Am. 
Chem.  Soc.,  29,  1709-18  (Dec.,  1907). 

( 64 )  KOVARDT,  A.  F.  and  L.  W.  McKJEEHAN,  "Radioactivity.    Report  of  Committee 

on  X-rays  and  Radioactivity,  National  Research  Council,"  National  Acad- 
emy of  Sciences,  Washington,  D.  C.,  1925,  203  pp. 

(65)  "Madame  Marie  Curie  dedicates  Hepburn  Hall  of  Chemistry  at  St.  Lawrence 

University,"  /.  Chem.  Educ.,  7, 268-76  (Feb.,  1930). 

(66)  "Editors  outlook.    Frederick  Soddy,"  ibid.,  8,  1245-6  (July,  1931). 

(67)  "Editor's  outlook.    Theodore  William  Richards,"  ibid.,  5,  783-4  (July,  1928). 


THE  NATURAL  RADIOACTIVE  ELEMENTS  841 

(68)  CURIE,  MME.,  "Pierre  Curie,"  ref.  (I),  p.  170. 

(69)  W.  R.  W.,  "Anniversaries  of  science,"  /.  Chem.  Educ.,  4,  400  (March,  1927). 

(70)  "Local  activities.     Cornell  University,"  ibid.,  7?  707  (March,  1930). 

(71)  MENDELEEV,    D.,    "Die   periodische   Gesetzmassigkeit   der    chemischen   Ele- 

mente,"  Ann.,  Suppl  VIII,  191  (1871). 

(72)  "Editor's  outlook.     Sir  Ernest  Rutherford  (1871-          ),"  J.  Chem.  Educ.,  7, 

493-4  (Mar.,  1930). 

(73)  HAHN,  O.,  "The  mother  substance  of  radium,"  Chem.  News,  96,  272-3  (Dec. 

6,  1907);  Ber.,  40,  4415-20  (1907). 

(74)  URBAIN,  G.,  "Discours  sur  les  Elements  Chimiques  et  stir  les  Atomes.     Hom- 

mage  au  Professeur  Bohuslav  Brauner,"  Rec.  trav.  chim.,  44,  285  (1925). 

(75)  "Les  Prix  Nobel  en  1921-1922,"  P.  A.  Norstedt  &  Soner,  Imprimerie  Royale, 

Stockholm,  1923,  pp.  1-29.  Soddy  on  "The  origins  of  the  conception  of 
isotopes." 

(76)  MARSDEN,  E.  and  T.  BARRATT,  "The  a-particles  emitted  by  the  active  deposits 

of  thorium  and  actinium,"  Proc.  Physical  Soc.,  24,  [1],  50-61  (1911); 
Physik.  Z.,  13,  193-9  (Mar.  1,  1912). 

(77)  MARCKWALD,  W.  and  KEETMAN,  "Notiz  iibea:  das  Ionium,"  Ber.,  41,  49-50 

(1908). 

(78)  RICHARDS,  T.  W.  and  M.  E.  LEMBERT,  "The  atomic  weight  of  lead  of  radio- 

active origin,"  J.  Am.  Chem.  Soc.,  36,  1329-44  (July,  1914). 

(79)  HONIGSCHMED,  M.  E.  and  S.  HOROVITZ,  "Sur  le  poids  atomique  du  plomb  de 

la  pechblende,"  Compt.  rend.,  158,  1796-8  (June  15,  1914). 

(80)  GEIGER,  H.  and  E.  MARSDEN,  "Number  of  alpha  particles  emitted  by  actinium 

and  thorium  emanations."  Physik.  Z.,  11,  7-11  (Jan.  1,  1910). 

(81)  HONIGSCHMID,  M.  E.  and  S.  HOROVITZ,  "?Air  Kenntnis  des  Atomgewiehtes  des 

Urans,"  Monat.,  37,  185-90  (Dec.  9,  1916). 

(82)  HAHN,  O.  and  L.  MEITNER,  "Nachweis  der  komolexen  Natur  von  Radium  C," 

Physik.  Z.,  10,  697-703  (Oct.  15,  1909). 

(83)  SODDY,  F.,  "The  Interpretation  of  Radium,"  ref.  (56),  p.  138. 

(84)  Ibid.,  pp.  192-3. 

(85)  BERGWITZ,  "Julius  Elster,"  Chem.-Zig.,  44,  457  (June  19,  1920). 

(86)  SZILARD,    B.,    "Die    diesjahrigen   Trager   der    Nobelpreise    fiir    Chemie    und 

Physik.  Frau  Pierre  Curie  und  ihr  Werk,"  Chem.~Ztg.,  35,  1361-2  (Dec.  9, 
1911). 

(87)  H.  B.  D.,  "Theodore  William  Richards,"  Proc.  Roy.  Soc.   (London),  121A, 

xxix-xxxiv  (1928). 

(88)  GROSSE,  A.  V.,  "The  rarest  metal  yet  obtained,"  Sci.  Am.,  142,  42-4  (Jan., 

1930).    Protactinium. 

(89)  R.  W.  L.?  "Prof.  Tadeusz  Godlewski,"  Nature,  110,  361  (Sept.  9,  1922). 

(90)  RUSSELL,  A.  S.,  "The  periodic  system  and  the  radio-elements,"  Chem.  News, 

107,  49-52  Qan.  31,  1913);  F.  SODDY,  ibid.,  107,  97-9  (Feb.  28,  1913); 
K.  FAJANS,  "Die  radioaktiven  Umwandlungen  und  das  periodische  System 
der  Elemente,"  Ber.,  46,  422-39  (1913). 

( 91 )  RAMSAY,  W.  and  R.  W.  GRAY,  "La  densite  de  Temanation  du  radium,"  Compt. 

rend.,  151,  126-8  (July  11,  1910). 

(92)  CURIE,  MAURICE,  "Sur  les  ecarts  de  poids  atomiques  obtenus  avec  le  plomb 

provenant  de  divers  mineraux,"  Compt.  rend.,  158,  1676-9  (June  8,  1914). 

(93)  BOLTWOOD,  B.  B.,  "The  radioactivity  of  thorium  minerals  and  salts,"  Am.  J. 

Sci.  [4],  21,  423  (June,  1906);  ibid.,  24,  95  (Aug.,  1907). 

(94)  SCHLUNDT,  H.,  "The  refining  of  mesothoriurn,"  J.  Chem.  Educ.,  8,  1267-87 

(July,  1931). 

(95)  GROSSE,  A.  V.,  "Metallic  element  91,"  J.  Am.  Chem.  Soc.,  56,  2200-1  (Oct., 

1934). 

(96)  WIECHERT,  E.,  "Julius  Elster,"  Nachrichten  Gesellsch.  Wiss.  Gottingen,  pp. 

53-60  (1921);  R.  POHL,  "Hans  Geitel,"  ibid.,  pp.  69-74  (1923-24). 

(97)  RUSSELL,  A.  S.,  "Mme.  Curie  memorial  lecture,"  J.  Chem.  Soc.,  1935,  654r-63. 


842  DISCOVERY  OF  THE  ELEMENTS 


(98)     CURIE,  EVE,  "Marie  Curie,  my  mother/'  Saturday  Evening  Post,  210  (Sept. 
4-Oct.  23,   1937);  Doubleday,  Doran  and  Co.,  Garden  City,  New  York, 
S93 
' 


1  93      S       DD 

(99)  RAMSTEDT,'  EVA,  "Marie  Curie  och  radium,"  P.  A.  Norstedt  &  Soner  Stock- 
Mm,  1932,  58  pp.;  "Marie  Sklodowska  Curie,"  Svenska  Fynkersamfundets 
Kosmos,  12,  10-44  (1934).  , 

(100)     STTEGLITZ,  J.,  "Herbert  Newby  McCoy,"  Ind.  Eng.  Chem.,  News  Ed.,  13, 

(JO!)  Ev?°A(  £  J/CHArlticK,  J-  J.  THOMSON,  W.  H.  BRAGG,  NIELS  Bom,  F.  SODDY 
E  N.  DA  C.  ANDRADE,  and  F.  E.  SMITH,  "The  Right  Hon.  Lord  Rutherford, 
Nature,  140,  746-54  (Oct.  30,  1937). 

(102)  GEIGER,  H.,  "Memories  of  Rutherford  at  Manchester,    Nature,  141,  244  (Feb. 

t       -I  QOQ  \ 

(103)  EVE  A.  S.,'"The  Macdonald  Physics  Building,  McGill  University,  Montreal," 

Nature,  74,  272-5  (  July  19,  1906  ). 

(104)  MEYER,  STEFAN,  A.'N.  SHAW,  N.  BOHR,  G.  VON  HEVESY,  M    LE  Due  DE 

BROGLIE,  J.  STARK,  O.  HAHN,  E.  FERMI,  WERTENSTEIN,  and  N.  KAPITZA, 
"Further  tributes  to  the  late  Lord  Rutherford,"  Nature,  140,  1047-54  (Dec. 
18  1937) 

(105)  MATOOIS,  ANDRE,  "Mile.  Eve  Curie,"  Vogue,  91,  7^7,  172  (Apr.  15,  1938). 

(106)  VON  SCHWEIDLER,  E.,  "Julius  Elster  und  Hans  Geitel  als  Forscher,    Naturw 

3  372-7  (July  16,  1915);  KARL  BERGWITZ,  "Julius  Elsters  und  Hans  Geitels 
Bedeutung  fur  die  atmospharische  Elektrizitat,"  ibid.,  3,  377-83  (July  16, 

(107)  "Award  of  the  Willard  Gibbs  Medal  to  H.  N.  McCoy,"  Chem.  Bull,  24,  207- 

24  (June,  1937).  .       „ 

(105)  McCoy,  H.  N,  and  W.  H.  Ross,  "The  specific  radioactivity  of  uranium,  J. 
Am.  Chem.  Soc.,  29,  1698-1708  (1907). 

(109)  BOLTWOOD,  B.  B.,  Nature,  75,  223  (  1906-7  )  ;  Am.  J.  Sci.  (  4  )  ,  25,  298  (  1908  )  . 

(110)  GEIGER,  H.  and  E.  RUTHERFORD,  "The  number  of  alpha-particles  emitted  by 

uranium  and  thorium  and  by  uranium  minerals,"  Phil  Mag.,  20,  691-8 

(111)  KLICKSTEIN,  H.  S.,  "Pierre  Curie.    An  appreciation  of  his  scientific  achieve- 

ments," /.  Chem.  Educ.,  24,  278-82  (June,  1947). 

(112)  WALL,  FLORENCE  E,,  "Wilhelm  Ostwald,"  /.  Chem.  Educ.,  25,  2-10  (Jan., 

(IIS)  JAFFE,  GEORGE,  "Recollections  of  three  great  laboratories,"  J.  Chem.  Educ., 
29,236-8  (May,  1952). 

(114)  CURIE,  MARIE,  "Pierre  Curie,"  ref.  (I),  pp.  98-100. 

(115)  HULUBEI,  H.  and  Y.  CAUCHOIS,  "A  stable  element  of  atomic  number  84, 

Compt.  rend.,  210,  761-3  (June  3,  1940). 

(116)  "Gmelir/s  Handbuch  der  anorganischen  Chemie,"  Vol.  31,  Verlag  Chemie, 

Berlin,  1928,  pp.  1-27.    History  and  occurrence  of  radium. 

(117)  SHOHL,  A.  T.,  "Mineral  Metabolism,"  Reinhold  Publishing  Corporation,  New 

York,  1939,  pp.  32-3,  96,  141,  145. 

(IIS)  MELLOR,  J.  W.,  "Comprehensive  Treatise  on  Inorganic  and  Theoretical 
Chemistry,"  Vol.  4,  Longmans,  Green  and  Co.,  London,  1923,  pp.  135-6. 

(119)  HEVESY,  G.  and  F.  PANETH,  ref,  (14),  pp.  163-4. 

(120)  CURIE,  MME.,  ref.  (1),  p.  129. 

(121)  CURIE,  I.,  "TTbe  atomic  weight  of  the  chlorine  in  certain  minerals,"  Compt. 

rend.,  172,  1025-8  (1921);  "Nuclear  gamma  rays  from  beryllium  and 
lithium,  excited  by  alpha  rays  from  polonium,"  ibid.,  193,  1412-4  (1931); 
"Nuclear  structure  and  radioactivity,"  Rev.  sci.,  73,  357  (1935). 

(122)  CURIE,  I.  and  C.  CHAMTE,  "The  radioactive  constant  of  radon,"  Compt.  rend., 

178,  1808-10  (1924). 

(123)  JOLIOT,  F.,  "Electrochemical  study  of  the  radioelements/'  /.  chim.  phys.,  27, 

119-62  (1930). 


THE  NATURAL  RADIOACTIVE  ELEMENTS  843 

(124)  CROWTHER,  J.  G.,  "Mine.  Curie  and  her  successors,"  The  Nineteenth  Century 

and  After,  116,  194-205  (Aug.,  1934). 

(125)  CURIE,  I.  and  F.  JOLIOT,  "The  emission  of  high-speed  protons  by  hydrogen 

compounds  under  the  influence  of  gamma  rays  of  high  penetration," 
Compt.  rend.,  194,  273-5  ( 1932 ) ;  "The  effect  of  the  absorption  of  gamma 
rays  on  the  projection  of  nuclear  radiation,"  ibid.,  194,  708-11  (1932); 
"The  projection  of  atoms  by  very  penetrating  radiation  excited  in  light 
nuclei,"  ibid.,  194,  876-7  (1932);  "The  nature  of  the  penetrating  radia- 
tion excited  in  light  nuclei  by  alpha  particles,"  ibid.,  194,  1229-32  (1932); 
"Evidence  for  the  neutron,"  Nature,  130,  57  (1932);  "Conditions  of  emis- 
sion of  neutrons  by  the  action  of  alpha  particles  on  the  light  elements," 
Compt.  rend.,  196,  397-9  (1933);  "Positive  electrons,"  ibid.,  196,  1105-7 
(1933);  "The  origin  of  positive  electrons,"  ibid.,  196,  1581-3  (1933); 
"Positive  electrons  of  transmutation,"  ibid.,  196,  1885-7  (1933);  "The 
complexity  of  the  proton  and  the  mass  of  the  neutron,"  ibid.,  197,  237-8 
(1933);  "Experimental  proofs  of  the  existence  of  the  neutron,  J.  phys. 
radium,  (7),  4,  21-33  (1933);  "Recent  researches  on  the  emission  of 
neutrons,"  ibid.,  (7),  4,  278-86  (1933);  "Electrons  of  materialization  and 
of  transmutation,"  ibid.,  (7),  4,  494-500  (1933);  "Chemical  separation 
of  new  radioelements  emitting  positive  electrons,"  Compt.  rend.,  198,  559- 
61  (1934);  "Mass  of  the  neutron,"  Nature,  133,  721  (1934);  "Artificial 
production  of  radioactive  elements.  Chemical  proof  of  the  transmutation 
of  elements,"  /.  phys.  radium,  (7),  5,  153-6  (1934);  "Neutrons  and  posi- 
trons, Artificial  radioactivity,"  Rev.  gen.  sci.,  45,  229-35  (1934). 

(126)  CURIE,  L,  F.  JOLIOT,  and  P.  SAVEL,  "Radiations  excited  by  alpha  rays  in  light 

elements,"  Compt.  rend.,  194,  2208-11  (1932). 

(127)  SHADDUCK,  H.  A.,  "The  neutron,"  /.  Chem.  Educ.,  13,  303-8  (July,  1936). 

(128)  JOLIOT,  F.  and  I.  CURTE,  "Un  nouveau  type  de  radio activite,"  Compt.  rend., 

198,  254-6  (Jan.  15,  1934);  "Artificial  production  of  a  new  kind  of  radio- 
element,"  Nature,  133,  201-2  (Feb.  10,  1934);  "Les  nouveaux  radio- 
elements.  Preuves  chimiques  des  transmutations,"  J.  chim.  phys,,  31, 
611-20  (Dec.  25,  1934). 

(129)  CURIE,  L,  F.  JOLIOT,  and  P.  PREISWERK,  "Radioelements  produced  by  bom- 

bardment with  neutrons.  New  type  of  radioactivity,"  Compt.  rend.,  198, 
2089-91  (1934). 

(130)  CURIE,  L,  H.  VON  HALBAN,  and  P.  PREISWERK,  "Artificial  formation  of  ele- 

ments of  an  unknown  radioactive  family  by  irradiation  of  thorium  with 
neutrons,"  Compt.  rend.,  200,  1841-3  (1935);  "Radioactive  elements 
formed  by  irradiation  of  thorium  with  neutrons,"  ibid.,  200,  2079-80 
(1935). 

(131)  JOLIOT,  F.,  A.  LAZARD,  and  P.  SAVEL,  "Synthesis  of  radio-elements  by  deu- 

terons  accelerated  by  means  of  an  impulse  generator,"  ibid.,  201,  826-8 
(1935). 

(132)  SEABORG,  G.  T.,  "Artificial  radioactivity,"  Chem.  Revs.,  27,  199-285  (Aug., 

1940). 

(133)  BOYER,  "Les  Prix  Nobel  de  1935.     Une  visite  a  M.  et  Mme.  Joliot-Curie, 

laureats  du  Prix  Nobel  de  Chimie,"  La  Nature,  63,  585-6  (Dec.  15,  1935). 

(134)  ANON.,  "Actinium  isolated,"  Chem.  Eng.  News,  27,  3240  (Oct.  31,  1949). 

(135)  OESPER,  RALPH  E.,  "Otto  Honigschmid,"  J.  Chem.  Educ.,  17,  562   (Dec., 

1940). 

( 136 )  Chem.  Eng.  News,  34, 1584  ( Apr.  2,  1956) . 

(137)  Ibid.,  35,  44  (Jan.  14,  1957);  37;  98-3  (Apr.  20,  1959). 

( 138 )  ROMER,  ALFRED,  "The  transformation  theory  of  radioactivity,"  Isis,  49,  3-12 

(March  1958). 


Couriestj    of    Lyman    C.    Newell 

Henry  Gwyn  Jeffreys  Moseley,  1887-1915.  English  physicist  who 
studied  the  X-ray  spectra  of  more  than  fifty  elements  and  discovered 
the  relation  existing  between  the  atomic  number  of  an  element  and 
the  frequency  of  the  X-rays  which  it  emits  when  bombarded  by 
cathode  rays.  At  the  age  of  twenty-seven  years  he  was  killed  while 
in  active  service  at  the  Dardanelles. 


Beyond  the  violet  seek  him,  for  there  in  the  dark  he  dwells, 
Holding  the  crystal  lattice  to  cast  the  shadow  that  tells 
How  the  heart  of  the  atom  thickens,  ready  to  burst  into  flower. 
Loosing  the  bands  of  Orion  with  heavenly  heat  and  power. 
He  numbers  the  charge  on  the  center  for  each  of  the  elements. 
That  we  named  for  gods  and  demons,   colors   and  tastes   and 
scents  .  .  .  (1). 

Atom  from  atom  yawns  as  far  as  moon  from  earth,  as  star  from 
star  .  .  .  (2). 


30 

Discoveries  by  X-ray  spectrum  analysis 


When  H.  G.  J.  Mvseley  discovered  the  simple  relationship  which 
exists  between  the  X-ray  spectrum  of  an  element  and  its  atomic 
number,  there  were  seven  unfilled  spaces  in  the  periodic  table. 
Elements  43,  61,  72,  75,  85,  87,  and  91,  were  yet  to  be  revealed. 
Element  91  (protactinium}  was  discussed  with  the  radioactive 
elements  in  Chapter  29.  In  1923  D.  Coster  and  G.  von  Hevesy 
showed  that  element  72,  hafnium,  is  widely  distributed  but  that 
it  had  escaped  detection  because  of  its  close  resemblance  to  zir- 
conium. Element  75  (rhenium)  was  announced  by  W.  and  I. 
Noddack  in  1925,  and  is  now  a  commercial  article. 


.Ithough  Mendeleev's  periodic  system  was  a  great  aid  in  the 
search  for  new  elements,  there  were  some  anomalies  that  it  did  not  explain. 
The  practical  atomic  weight  of  argon,  for  example,  is  higher  than  that 
of  potassium,  yet  argon  must  precede  potassium  in  the  table,  for  there 
is  no  doubt  whatever  that  it  is  an  inert  gas  like  helium  and  that  potassium 
is  an  alkali  metal  like  sodium.  Tellurium  and  iodine  present  a  similar 
discrepancy,  and  the  radioactive  isotopes  were  also  the  cause  of  much 
perplexity. 

A  much  better  basis  of  classification  for  the  elements  was  finally 
found  by  a  young  English  physicist  in  the  course  of  his  researches  on 
X-rays.  Henry  Gwyn  Jeffreys  Moseley  was  born  at  Weymouth  on 
November  23,  1887.  While  he  was  still  a  very  young  child  he  had  the 
misfortune  to  lose  his  father,  a  distinguished  zoologist  and  professor  at 
Oxford  University.  Moseley  studied  at  Eton  and  at  Trinity  College, 
Oxford,  and  received  his  master's  degree  in  1910.  A  year  before  his 
graduation  he  went  to  Manchester  to  discuss  with  Sir  Ernest  Rutherford 
the  possibility  of  undertaking  original  research  in  physics  (3). 

After  serving  the  University  of  Manchester  for  two  years  as  lecturer 
and  demonstrator  in  physics,  he  resigned  his  position  in  order  to  devote 
all  his  time  to  research,  and  was  awarded  the  John  Harling  Fellowship. 
His  colleagues  soon  recognized  his  superiority  as  an  experimenter,  and 
admired  him  because  of  his  marvelous  technique,  broad  knowledge  of 
physics,  cheerfulness,  and  friendly  cooperation.  When  the  British  Associ- 
ation met  in  Australia  in  1914,  he  entered  enthusiastically  into  the  dis- 

845 


846  DISCOVERY  OF  THE  ELEMENTS 

cussion  of  atomic  structure  and  gave  an  excellent  report  of  his  own 
researches  on  the  X-ray  spectra  of  the  rare  earths  (4). 

No  scientist  of  the  first  rank  ever  had  a  shorter  career.  When  Great 
Britain  entered  the  war  he  immediately  returned  to  England,  entered  the 
military  service  as  a  signaling  officer,  and  on  June  13,  1915,  left  for  the 
Dardanelles.  On  the  10th  of  August,  when  he  was  telephoning  an  order 
to  his  division,  a  Turkish  bullet  passed  through  his  head.  His  will,  made 
while  he  was  in  active  service,  bequeathed  all  his  apparatus  and  much 
of  his  private  fortune  to  the  Royal  Society.  Although  Moseley  was  not 
quite  twenty-eight  years  old  at  the  time  of  his  death,  his  researches  had  so 
revolutionized  the  study  of  atomic  structure  that  his  name  will  endure 
forever  in  the  annals  of  science  (5?  6,  7,  8). 

Before  entering  the  military  service  he  had  become  intensely 
interested  in  Professor  Max  von  Laue's  discovery  that  "the  ordered 
arrangement  of  the  atoms  in  a  crystal  would  do  the  same  for  X-rays  that 
a  diffraction  grating  does  for  light"  (9).  When  a  target,  or  anticathode, 
is  bombarded  with  cathode  rays,  it  emits  a  beam  of  X-rays  which  is 
characteristic  of  the  substance  of  which  the  target  is  made.  With  the 
help  of  Mr.  C.  G.  Darwin,  a  grandson  of  the  famous  biologist,  Moseley 
mapped  the  high-frequency  spectrum  of  an  X-ray  tube  provided  with  a 
platinum  anticathode  (9). 

In  the  hope  of  finding  some  relationship  between  the  frequency  of 
the  rays  and  the  atomic  number,  or  ordinal  number  of  the  element  in 
the  periodic  table,  he  then  carried  out  an  elaborate  investigation  in  which 
many  different  elements  served  as  anticathodes.  Upon  examining  these 
rays  by  diffracting  them  through  a  crystal,  he  found  the  following  simple 
and  beautiful  relationship:  When  all  the  known  elements  are  numbered 
in  the  order  of  their  positions  in  the  periodic  system,  the  square  root  of  the 
frequency  of  the  X-rays  emitted  is  directly  proportional  to  the  atomic 
number. 

Thus  Moseley's  series  is  almost  the  same  as  Mendeleev's  series  of 
increasing  atomic  weights.  When,  however,  the  elements  are  arranged, 
not  according  to  their  atomic  weights,  but  according  to  their  atomic 
numbers  (Moseley  numbers),  the  discrepancies  between  argon  and  potas- 
sium and  between  iodine  and  tellurium  disappear  (10). 

Moseley's  work  not  only  shed  much  light  on  the  periodic  system  and 
the  relationships  between  known  elements  and  the  radioactive  isotopes, 
but  was  also  a  great  stimulus  in  the  search  for  the  few  elements  remaining 
undiscovered  (II).  One  of  the  first  chemists  to  utilize  the  new  method 
was  Professor  Georges  Urbain  of  Paris,  who  took  his  rare  earth  prepara- 
tions to  Oxford  for  examination.  Moseley  showed  him  the  characteristic 
lines  of  erbium,  thulium,  ytterbium,  and  lutetium,  and  confirmed  in  a  few 
days  the  conclusions  which  Professor  Urbain  had  made  after  twenty  years 


DISCOVERIES  BY  X-EAY  SPECTRUM  ANALYSIS 


847 


Courtesy  Prof.  K.  Freuderiberg 

Max  von  Laue,  1879-1960.    German  physicist  who  in  1912  discovered  the 
interference  of  X-rays  diffracted  by  crystals,  measured  the  wave  lengths 
of  X  rays,  and  studied  the  structure  of  crystals.    In  1914  he  was  awarded 
the  Nobel  Prize  for  physics. 


848  DISCOVERY  OF  THE  ELEMENTS 

of  patient  research.  The  latter  was  greatly  surprised  to  find  that  a  sci- 
entific contribution  of  such  fundamental  importance  had  been  made  by 
one  so  young,  and  immediately  began  to  teach  Moseley's  method  of  X-ray 
analysis.  "His  law,"  said  he,  "substituted  for  the  rather  romantic  classifi- 
cation of  Mendeleev  a  precision  entirely  scientific"  (6). 

A.  V.  Grosse  (12)  has  shown,  however,  that,  when  one  substitutes  for 
the  practical  atomic  weight  of  each  element  the  arithmetic  mean  of  the 
atomic  weights  of  all  its  isotopes,  "the  row  of  increasing  atomic  weights  is 
identical  with  the  sequence  of  increasing  nuclear  charges"  and  the 
discrepancies  formerly  presented  by  argon  and  potassium,  cobalt  and 
nickel,  tellurium  and  iodine,  and  thorium  and  protactinium  no  longer  exist. 

HAFNIUM  (Element  72) 

Moseley  stated  that,  within  the  limits  of  his  researches,  which  covered 
all  the  elements  between  aluminum  (number  13)  and  gold  (number  79), 
there  were  spaces  for  three  missing  ones;  numbers  43,  61,  and  75,  and 
that,  since  their  X-ray  spectra  can  he  accurately  predicted,  it  ought  to  be 
rather  easy  to  find  them.  It  was  then  believed  that  the  celtium  whose  arc 
spectrum  Professor  Urbain  had  described  in  1911  was  element  72  (6, 
13,14). 

However,  when  Moseley  and  Urbain  examined  the  rare-earth  residues 
supposed  to  contain  the  new  element,  they  found  only  about  ten  lines, 
all  of  which  could  be  attributed  to  lutetium  and  ytterbium.  In  1922,  after 
a  long  period  of  interruption  because  of  military  duties,  Professor  Urbain 
resumed  his  search  for  element  72  in  the  same  rare-earth. residues  which 
he  and  Moseley  had  examined  before  the  war.  At  his  suggestion  M.  A. 
Dauvillier  used  de  Broglie's  improved  method  of  X-ray  analysis  and 
observed  two  faint  lines  which  almost  coincided  with  those  predicted  for 
element  72  (15,  16). 

After  titanium  was  discovered  in  1791  by  the  Reverend  William 
Gregor  in  Cornwall,  its  atomic  weight  was  determined  by  such  able 
chemists  as  H.  Rose,  C.  G.  Mosander,  and  J.-B.-A.  Dumas,  but  the  results 
showed  such  great  discrepancies  that  Mendeleev  predicted  that  another 
element  would  be  found  in  titanium  ores  (17). 

When  Edgar  Fahs  Smith  was  investigating  monazite  sand  under  the 
direction  of  F.  A.  Genth  ( 1820-1893 ) ,  the  latter  always  appropriated  the 
zirconium  sulfate  that  was  extracted,  and  would  say  as  he  carried  it 
away,  "Zirconium  is  not  simple;  there  is  another  element  concealed  in 
it,  and  when  I  have  leisure  I  shall  endeavor  to  isolate  it"  (18).  It  was  in 
zirconium  ores  that  large  quantities  of  element  72  were  first  revealed 
(19,20,21). 

Since  zircon  often  contains  small  amounts   of  other  elements   in 


DISCOVERIES  BY  X-RAY  SPECTRUM  ANALYSIS 


849 


addition  to  the  zirconium,  silicon,  and  oxygen  which  are  essential  to 
its  composition,  announcements  appeared  from  time  to  time  of  the  com- 
plexity of  zirconium,  and  several  "new  elements"  were  announced  which 
were  later  proved  to  be  false  (22). 

On  the  basis  of  his  quantum  theory  of  atomic  structure,  Niels  Bohr 
believed  that,  since  Urbain's  celtium  had  been  obtained  from  the  rare 
earths,  it  could  not  be  element  72,  for  the  latter  must  be  quadrivalent 
rather  than  trivalent  and  must  belong  to  the  zirconium  family.  He  showed 
that  the  chemical  properties  of  an  atom  are  determined  by  the  number 
and  arrangement  of  the  electrons  within  it  and  especially  by  the  number 


Georg  von  Hevesy.  Hungarian  chem- 
ist who,  with  Dr.  Dirk  Coster  of  the 
University  of  Groningen,  discovered  the 
element  hafnium  in  zirconium  ores  and 
made  a  thorough  study  of  its  properties. 
Author  of  many  papers  on  chemical 
analysis  by  X-rays,  radioactivity,  the 
rare  earths,  and  electrolytic  conduction. 
In  1943  he  was  awarded  die  Nobel 
Prize  in  Chemistry  and  in  1959  he  re- 
ceived the  Atoms  for  Peace  Award. 


Courtesy    Cornell    University 


and  arrangement  of  the  outermost  ones,  the  so-called  "valence  electrons." 
Since-  there  is  usually  an  appreciable  difference  in  the  outer  electrons  of 
two  adjacent  elements  in  the  periodic  system,  there  is  also,  as  a  rule,  a 
marked  difference  in  chemical  properties.  In  the  rare-earth  group,  how- 
ever, and  in  the  triads  of  the  iron  and  platinum  families,  the  only  structural 
differences  are  in  the  deeper  shells  of  the  atoms,  and  therefore  these 
elements  are  more  difficult  to  separate.  According  to  Bohr's  theory  these 
deep-seated  differences  in  the  rare  earths  lie  in  the  interval  between 
lanthanum  ( element  57 )  and  lutetium  ( element  71 ) .  Element  72  should, 
however,  according  to  his  theory,  be  quite  different  from  lutetium  in  the 
constitution  of  its  outer  group  of  electrons,  and  should  therefore  exhibit 


850 


DISCOVERY  OF  THE  ELEMENTS 


properties  entirely  different  from  those  of  the  rare  earth  elements  (16), 
but  closely  resembling  those  of  zirconium.  Bohr  therefore  advised  Dr. 
Georg  von  Hevesy  to  search  for  this  element  in  zirconium  ores  (23,  24), 
It  was  in  January,  1923,  that  Dirk  Coster  and  Georg  von  Hevesy  in 
Copenhagen  brought  their  search  for  the  new  member  of  the  zirconium 
family  to  a  successful  conclusion.  Its  discovery  in  a  Norwegian  zircon  and 
later  in  all  the  zirconium  minerals  and  all  the  commercial  zirconium 
preparations  they  investigated,  even  those  which  had  previously  been 
believed  to  be  pure,  was  made  possible  by  Moseley's  method  of  X-ray 
analysis,  and  it  was  Coster's  previous  work  in  the  same  field  that  enabled 
him  to  recognize  the  new  element  (5). 


Dirk  Coster.  Professor  of  physics  and 
meteorology  at  the  Royal  University  of 
Groningen.  Co-discoverer  with  Georg  von 
Hevesy  of  the  element  hafnium.  Author 
of  many  papers  on  X-rays  and  atomic 
structure. 


Although  they  named  it  hafnium*  for  the  city  of  Copenhagen,  neither 
of  these  investigators  is  Danish.  Professor  Coster  is  a  professor  of  physics 
and  meteorology  at  the  Royal  University  of  Groningen  and  director  of 
the  physical  laboratory.  The  Dutch,  French,  English,  German,  and 
American  journals  contain  many  of  his  papers  on  such  subjects  as  X-ray 
spectra,  theory  of  atomic  structure,  Stokes's  law  in  the  L-series  of  X-rays, 
and  the  rotational  oscillation  of  a  cylinder  in  a  viscous  liquid. 

Professor  von  Hevesy  was  born  in  Budapest  in  1885  and  was  educated 
in  the  universities  of  Budapest,  Berlin,  and  Freiburg.  His  researches 

*  Both  sides  of  the  controversy  regarding  the  name  of  element  72  are  presented  in 
the  English  journals,  Nature  and  Chemistry  and  Industry  (16,  24). 


DISCOVERIES  BY  X-RAY  SPECTRUM  ANALYSIS  851 

have  brought  him  into  close  contact  with  such  famous  scientists  as  Fritz 
Haber  at  Karlsruhe,  Lord  Rutherford  at  Manchester,  and  F.  G.  Donnan  at 
Liverpool,  and  the  X-ray  investigation  with  Dr.  Coster  which  resulted  in 
the  discovery  of  hafnium  was  carried  out  while  both  were  connected  with 
Bohr's  Institute  of  Theoretical  Physics  at  Copenhagen.  Professor  von 
Hevesy  has  served  on  the  faculties  of  the  University  of  Freiburg  and  the 
Research  Institute  of  Organic  Chemistry  of  Stockholm,  and  in  1930  was 
a  visiting  lecturer  at  Cornell  University.  His  researches  have  been 
carried  out  in  the  fields  of  physical  chemistry,  electrochemistry,  radio- 
activity, and  the  separation  of  isotopes  (25) . 

Hafnium  had  lain  hidden  for  untold  centuries,  not  because  of  its 
rarity  but  because  of  its  close  similarity  to  zirconium  (16},  and  when 
Professor  von  Hevesy  examined  some  historic  museum  specimens  of 
zirconium  compounds  which  had  been  prepared  by  Julius  Thomsen,  C.  F. 
Rammelsberg,  A.  E.  Nordenskjold,  J.-C.  G.  de  Marignac,  and  other  experts 
on  the  chemistry  of  zirconium,  he  found  that  they  contained  from  1  to  5 
per  cent  of  the  new  element  (26,  27).  The  latter  is  far  more  abundant 
than  silver  or  gold.  Since  the  earlier  chemists  were  unable  to  prepare 
zirconium  compounds  free  from  hafnium,  the  discovery  of  the  new  element 
necessitated  a  revision  of  the  atomic  weight  of  zirconium  (24,  28).  Some 
of  the  minerals  were  of  nepheline  syenitic  and  some  of  granitic  origin 
(20).  Hafnium  and  zirconium  are  so  closely  related  chemically  and  so 
closely  associated  in  the  mineral  realm  that  their  separation  is  even  more 
difficult  than  that  of  niobium  (columbium)  and  tantalum  (29).  The 
ratio  of  hafnium  to  zirconium  is  not  the  same  in  all  minerals. 

Professor  von  Hevesy  and  Thai  Jantzen  separated  hafnia  from  zirconia 
by  repeated  recrystallization  of  the  double  ammonium  or  potassium 
fluorides  (20,  26).  Metallic  hafnium  has  been  isolated  and  found  to 
have  the  same  crystalline  structure  as  zirconium.  A  small  specimen  of 
the  first  metallic  hafnium  ever  made  is  on  permanent  display  at  the 
American  Museum  of  Natural  History  in  New  York  City.  Dr.  von  Hevesy, 
who  prepared  it,  presented  it  to  the  Museum  for  the  collection  of  chemical 
elements  (29).  A.  E.  van  Arkel  and  J.  H.  de  Boer  prepared  hafnium  by 
passing  the  vapor  of  the  tetraiodide  over  a  heated  tungsten  filament 
(26,30). 

RHENIUM  (Element  75) 

Two  new  elements  of  the  manganese  group,  numbers  43  (eka- 
manganese)  and  75  (dwi-manganese),  were  announced  in  June,  1925,  by 
the  German  chemists  Dr.  Walter  Noddack  and  Dr.  Ida  Tacke  of  the 
Physico-Technical  Testing  Office  in  Berlin  and  Dr.  Otto  Berg  of  the 
Werner-Siemens  Laboratory.  The  discovery  was  not  accidental,  but  the 


852  DISCOVERY  OF  THE  ELEMENTS 

result  of  a  long  search  begun  in  1922  in  platinum  ores  and  later  in  sulfide 
ores  and  in  the  mineral  columbite  (31).  Platinum  ores  contain  the 
elements  24  to  29,  44  to  47,  and  76  to  79  (chromium  to  copper,  ruthenium 
to  silver,  and  osmium  to  gold),  whereas  columbite  contains  numbers  39 
to  42  and  72  to  74  (yttrium  to  molybdenum,  and  hafnium  to  tungsten). 
Hence  it  was  hoped  that  one  or  both  of  these  sources  might  yield  the 
missing  elements,  43  and  75. 

Upon  studying  the  relative  frequencies  of  known  elements  in  the 
earth's  crust,  Noddack,  Tacke,  and  Berg  found  that  those  of  odd  atomic 
number  are  less  common  than  those  of  even  number,  and  from  the  known 
frequency  of  occurrence  of  platinum  ores  and  of  columbite  they  obtained 
an  approximate  idea  of  the  extent  to  which  they  would  have  to  carry 
their  processes  of  extraction.  Moreover,  since  elements  43  and  75  were 
believed  to  belong  to  the  manganese  group,  many  of  their  physical  and 
chemical  properties  could  be  predicted.  In  May,  1925,  Noddack  and 
Tacke  and  Dr.  O.  Berg  of  the  Siemens  and  Halske  Company  accomplished 
a  100,000-fold  concentration  of  element  75  in  a  gadolinite,  and  by  careful 
measurement  of  five  lines  of  the  L-series  of  its  X-ray  spectrum  established 
the  existence  of  this  new  element  (36).  Element  75  was  finally  separated 
from  columbite,  and  named  rhenium  in  honor  of  the  German  Rhine  (32, 
33).  The  difficult  concentration  processes  were  carried  out  by  Drs. 
Noddack  and  Tacke  alone,  but  Dr.  Berg  assisted  in  making  the  observa- 
tions with  the  X-ray  spectroscope  .(34).  They  also  observed  some  X-ray 
lines  which  they  attributed  to  element  43,  which  they  named  masurium  for 
Masurenland,  East  Prussia.  The  history  of  element  43  will  be  given  in 
Chapter  31.  Before  the  discovery  of  rhenium,  manganese  had  no  com- 
panions in  sub-group  Vila  of  the  periodic  system. 

On  September  5,  1925,  Fraulein  Tacke  lectured  on  the  new  elements 
before  the  Verein  deutscher  Chemiker  in  Nuremberg  (35).  After  thank- 
ing her  for  the  address,  the  president  mentioned  that  this  was  an  historic 
occasion,  for  it  was  the  first  time  that  a  woman  had  ever  spoken  before 
the  Verein.  He  also  expressed  the  hope  that  other  "  Chemiker  inneri" 
might  soon  follow  her  example.  Fraulein  Tacke  and  Dr.  Noddack  have 
since  been  united  in  marriage  and  have  continued  their  joint  researches. 
Largely  through  their  efforts,  the  knowledge  of  rhenium  has  rapidly 
increased,  and  the  chemical,  physical,  and  analytical  properties  of  a  large 
number  of  its  compounds  have  been  accurately  determined.  In  recogni- 
tion of  their  discoveries  they  were  awarded  the  Liebig  Medal.  They 
found  that  Scandinavian  sulfide  ores  of  iron,  copper,  and  molybdenum 
are  a  far  more  suitable  source  of  rhenium  than  are  native  platinum  ores 
(36).  Because  of  its  scarcity,  rhenium  could  not  be  detected  by  direct 
physical  or  chemical  means  in  ores,  minerals,  or  technical  products.  By 
working  up  660  kilograms  of  molybdenite,  the  discoverers  of  rhenium 


DISCOVERIES  BY  X-RAY  SPECTRUM  ANALYSIS 


853 


nevertheless  succeeded  in  1928  in  preparing  a  gram  of  it.  In  the  following 
year  they  extracted  an  additional  1.7  grams  of  it  from  pyrrhotite  (magnetic 
pyrites)  and  molybdenite,  which  enabled  them  to  investigate  its  prop- 
erties. Since  the  process  of  extracting  rhenium  from  minerals  was  too 
expensive  to  permit  production  on  a  larger  scale,  the  Noddacks  investi- 
gated a  number  of  technical  products  in  search  of  one  which  might  contain 
rhenium  in  higher  concentrations.  Near  the  end  of  1929  W.  Feit  pre- 
sented them  with  a  molybdenum  sulfide  solution  containing  1.5  per  cent 


Jaroslav  Heyrovsky,  1890-  .  Profes- 
sor of  physical  chemistry  at  Charles  Uni- 
versity, Prague.  Author  of  an  "Intro- 
duction to  Radioactivity."  With  E. 
Votocek  he  founded  the  Collection  of 
Czechoslovak  Chemical  Communica- 
tions, a  monthly  journal  published  in 
French  and  English  to  make  the  con- 
tributions of  Czechoslovakian  and  Rus- 
sian chemists  accessible  to  those  who 
do  not  read  the  Slavonic  languages.  In 
1959  he  was  awarded  the  Nobel  Prize  in 
Chemistry. 


of  rhenium.  Since  the  raw  material,  a  residue  already  in  technical  use, 
contained  ten  times  as  much  rhenium  as  the  richest  ore,  Feit  soon 
developed  a  commercial  process  which  made  possible  the  production  of 
several  hundred  grams  of  potassium  perrhenate  (36). 

Molybdenite  from  a  mine  at  Middle  Inlet,  Marinette  County,  in 
northern  Wisconsin  was  found  to  contain  relatively  large  amounts  of 
rhenium  (37). 

In  1925  F.  H.  Loring  and  J.  G.  F.  Druce  in  England  and  V.  Dolejsek 
and  J.  Heyrovsky  in  Czechoslovakia  independently  announced  that  com- 
mercial manganese  salts  and  even  so-called  "pure"  preparations  contain 
small  amounts  of  element  75  (38, 39,  40) .  While  searching  for  an  element 
of  atomic  number  93,  the  English  chemists  removed  manganese  and  other 
heavy  metals  by  precipitation  as  the  sulfides,  and  evaporated  the  filtrate  to 
dryness.  X-ray  analysis  of  the  residue  apparently  revealed  lines  of 
element  75. 


854 


DISCOVERY  OF  THE  ELEMENTS 


Dr.  J.  Heyrovsky,  professor  of  physical  chemistry  at  the  Charles 
University  of  Prague,  and  Dr.  Dolejsek  of  the  Prague  Academy  of  Sciences 
thought  they  detected  element  75  in  manganese  salts  by  a  different  method. 
They  examined  some  manganese  solutions  with  their  dropping  mercury 
cathode,  plotted  the  current  intensity  as  ordinates  against  the  applied 
electromotive  force  as  abscissas,  and  noticed  a  peculiar  "hump"  in  the 
curve  in  the  region  between  —1.00  and  —1.19  volts  from  the  potential 
of  the  calomel  electrode.  After  showing  that  zinc,  nickel,  cobalt,  and 


William    Frederick    Meggers. 

Physicist  at  the  U.  S.  Bureau 
of  Standards  since  1914. 
Chief  of  the  spectroscopy  sec- 
tion. Author  of  many  papers 
on  optics,  astrophysics,  pho- 
tography, measurement  of 
wave-length  standards,  and 
description  and  analysis  of 
spectra.  The  instrument  in 
the  foreground  is  a  concave 
grating  spectrograph,  used  for 
photographing  the  emission 
spectrum  of  rhenium  ( 41 ) . 


Courtesy  Scientific  Monthly 


iron  were  absent,  Heyrovsky  and  Dolejsek  suspected  the  presence  of  the 
undiscovered  eka-manganeses,  elements  43  and  75.  Using  their  dropping 
mercury  cathode  in  conjunction  with  a  polarograph,  they  obtained  auto- 
matically a  permanent  record  of  the  electrolytic  reaction. 

After  dipping  strips  of  zinc  into  concentrated  solutions  of  manganese 
salts,  they  scraped  off  a  deposit  containing  zinc,  lead,  cadmium,  nickel,  and 
cobalt.  After  complete  removal  of  these  heavy  metals  by  precipitation  as 
the  sulfides,  they  found  no  evidence  of  element  43,  but  thought  they 
found  the  X-ray  lines  of  number  75  (42).  When  Dr.  Druce  took  his 
dwi-manganese  preparation  to  the  Charles  University  in  Prague  for  polaro- 
graphic  examination,  the  Czechoslovakian  chemists  confirmed  his  con- 
clusions. 


DISCOVERIES  BY  X-RAY  SPECTRUM  ANALYSIS  855 

In  response  to  criticism  by  the  Noddacks  and  by  L.  C.  Kurd  (43), 
who  was  unable  to  detect  rhenium  in  any  of  the  various  manganese  salts 
which  he  studied.  Dr.  Heyrovsky  himself  afterward  worked  out  a  sensitive 
polarographic  test  for  the  absence  of  rhenium  in  manganese  salts.  Al- 
though potassium  perrhenate  gives  a  polarographic  step  at  —1.2  volts  from 
the  normal  calomel  zero,  this  is  not  conclusive  evidence  for  rhenium  in 
presence  of  cobalt,  iron,  nickel,  or  zinc,  When,  however,  he  added  sodium 
acetate,  acetic  acid,  and  hydrogen  sulfide  to  precipitate  these  metals,  the 
perrhenate  was  changed  to  Re2S7  or  thioperrhenate,  without  precipitating, 
and  the  "step"  was  shifted.  In  the  absence  of  perrhenate,  this  shift  does 
not  occur.  Upon  testing  various  commercial  manganese  salts  in  this 
manner,  Professor  Heyrovsky  found  that  they  contain  less  than  one  part 
of  rhenium  per  million  parts  of  manganese  and  that  the  polarograph  steps 
at  —1.0  and  —1.2  volts  shown  on  polarograms  of  manganese  solutions,  as 
well  as  the  lines  of  the  X-ray  spectrum,  must  be  due  to  elements  other 
than  rhenium  (44).  Although  the  polarograms  were  at  first  misinterpreted 
in  this  case,  the  polarographic  method  has  nevertheless  been  used  suc- 
cessfully in  other  analyses  (45).  . 

According  to  the  well-founded  rules  of  Josef  Mattauch,  no  stable 
isotopes  of  element  43  are  to  be  expected.  This  may  explain  why  it  has 
never  been  prepared  and  concentrated  from  natural  products  (46). 

Colin  G.  Fink  and  P.  Deren  of  Columbia  University  in  1934  perfected 
a  process  for  electroplating  rhenium  as  a  bright,  hard  deposit  which  is 
surprisingly  resistant  to  hydrochloric  acid  (47).  Dr.  William  F.  Meggers 
of  the  United  States  Bureau  of  Standards  has  made  a  thorough  study  of 
the  arc  spectrum  of  rhenium  (41). 


LITERATURE  CITED 

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(2)  Journals  of  R.  W.  Emerson,  Centenary  Ed.,  Vol.  VI,  Houghton,  Miffln  Co., 

p.  207;  See  also  C.  A.  BROWNE,  "Emerson  and  chemistry/'  /.  Chem.  Educ., 
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(3)  RUTHERFORD,  E.,  "Henry  Gwyn  Jeffreys  Moseley,"  Nature,  96,  33-4  (Sept.  9, 

1915). 

(4)  "Discussion  on  the  structure  of  atoms  and  molecules,"  Brit.  Assoc.  Reports,  84, 

293-301  (Aug.  18,  1914). 

(5)  POGGENDORFF,   J.    C.,   "Biographisch-Literarisches   Handwb'rterbuch  zur   Ge- 

schichte  der  exakten  Wissenschaften,"  6  vols.,  Verlag  Chemie,  Leipzig  and 
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xxii-xxviii  (1917). 

(7)  LANKESTER,  SIR  E.  RAY,  "Henry  Gwyn  Jeffereys  Moseley,"  Phil.  Mag,,  31, 

173-6  (Feb.,  1916). 

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(1927). 


856  DISCOVERY  OF  THE  ELEMENTS 

191 


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(  14  )     ui          G.,  "Sur  un  nouvel  element  qui  accompagne  le  lutecium  et  le  scandium 
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(16)  ANON.,  "The  new  element  hafnium"  Chem.  &  Ind.   (N.  S.)    42,  67   (Jan 

26  1923);  D.  COSTEH  and  G.  HEVESY,  ibid.,  258  (Mar.  18  1923);  Editorial, 
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(18)  BROWNE,  C.  A.  (  editor)  ,  "A  Half-Century  of  Chemistry  in  America,  1870-1926, 

"Am.  Chem.  Soc.,  Philadelphia,  1926,  p.  72. 

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(20)  HEVESY,  G.,  "The  discovery  and  properties  of  hafnium,"  Chem.  Reviews,  2, 

1^41  (Apr.,  1925). 

(21)  "The  newer  metals  of  group  IV.    A  classic  of  science,    Sci.  News  Letter,  21, 

166-8  (Mar.  12,  1932). 

(22)  VENABLE,  F.  P.,  "Zirconium  and  Its  Compounds/  Chem.  Catalog  Co.,  New 

York,  1922,  173pp. 

(23)  HOPKINS,  B.  S.,  "Building  blocks  of  the  universe,    Set.  Am.,  136,  87-9  (Feb., 

1927  ) 

(24)  URBAIN    G.,  and  A.  DAUVIIXIER,  "On  the  element  of  atomic  number  72," 

Nature,  111,  218  (Feb.  17,  1923);  D.  COSTER  and  G.  HEVESY,  "On  the 
new  element  of  atomic  number  72,"  ibid.,  Ill,  79   (Jan.  20,  1923);   182 
(Feb.  10,  1923);  252  (Feb.  24,  1923). 
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(26)  MELLOR,  J.  W.  "Comprehensive  Treatise  on  Inorganic  and  Theoretical  Chem- 

istry,"' Vol.  7,  Longmans,  Green  and  Co.,  New  York,  1927,  pp.  166-70 
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zirconium  preparations,"  Nature,  113,  384-5  (Mar.  15,  1924). 

(27)  HEVESY,    G.,    "Recherches    sur   les    proprietes    du    hafnium,"    Kgl.    Danske 

Videnskab.  Selskab,  Mat.-fys.  Medd.,  6,  3-149  (1925).     In  French. 

(28)  "Hafnium,"  Sci.  Mo.,  25,  285-8  (Sept.,  1927). 

(29)  LEE,  O.  IVAN,  "The  mineralogy  of  hafnium,"  Chem.  Reviews,  5,  17-37  (Feb., 

1928). 

(30)  VAN  ABKEL,  A.  E.,  and  J.  H.  DE  BOER,  "Darstellung  von  reinen  Titanium-, 

Zirkonium-,  Hafnium-,  and  Thoriummetall,"  Z.  anorg.  Chem.,  148,  345-50 
(Oct.  29,  1925). 


DISCOVERIES  BY  X-RAY  SPECTRUM  ANALYSIS  857 

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NODDACK,  "Die  .Sauerstoffverbindungen  des  Rheniums,"  Z.  anorg.  Chem., 
((  181,  1-37  (Heft  1,  1929);  Chem.  News,  131,  84-7  (Aug.  7,  1925). 

(32)  "Two  new  elements  of  the  manganese  group,"  Nature,  116,  54-5  (July  11, 

1925). 

(33)  NODDACK,  W.,  and  I.  NQDDACK,  "tfber  den  Nachweis  der  Ekamangane,"  Z. 

angew.  Chem.,  40,  25CM  (Mar.  3,  1927). 

(34)  BERG,  O.,  trber  den  rontgenspektroskopischen  Nachweis  der  Ekamangane,"  Z. 

angew.  Chem.,  40,  254-6  (Mar.  3,  1927). 

(35)  TACKE,  I.,  "Zur  Auflmdung  der  Ekamangane,"  Z.  angew.   Chem.,  38,  794 

(Sept.  10,  1925);  1157-60  (Dec.  17,  1925). 

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86  pp. 

(37)  WORKS,  MRS.  L.  P.,  "A  rhenium-bearing  molybdenite  in  northern  Wisconsin," 

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for  1929,  pp.  245-51;  Sci.  Progress,  20,  109-14  (July,  1926);  Scientia,  43, 
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dwimanganese  in  manganese  salts,"  Nature,  1,17,  159  (Jan.  30,  1926). 

(40)  DRUCE,  J.   G.   F.,   "Examination  of  crude  manganese  compounds  and  the 

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spectrum  of  rhenium,"  Bur.  Standards  J.  Research,  6,  1027-50  (June,  1931). 

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75)  in  manganese  salts,"  Nature,  116,  782-3  (Nov.  28,  1925);  J.  HEYROVSKY, 
ibid.,  117,  16  (Jan.  2,  1926);  Science  (N.  S.),  62,  Suppl.  xiv  (Nov.  20, 
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(43)  KURD,  L.  C.,  "The  discovery  of  rhenium,"  J.  Chem.  Educ.,  10,  605-8  (Oct., 

1933);  J.  G.  F.  DRUCE,  ibid.,  11,  59  (Jan.,  1934). 

(44)  HEYROVSKY,  J.,  "A  sensitive  polarographic  test  for  the  absence  of  rhenium  in 

manganese  salts,"  Nature,  135,  870-1  (May  25,  1935). 

(45)  HERMAN,   J.   "The  polarograph,   a  valuable  tool  in   quantitative   chemical 

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(46)  SEGRE,  E.,  "Artificial  radioactivity  and  the  completion  of  the  periodic  system 

of  the  elements,"  Sci.  Mo.,  57,  12-16  (July,  1943). 

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Courtesy  Chemical  and  Engineering  News 

E.  0.  Lawrence,  G.  T,  Seaborg,  and  J.  R.  Oppenheimer 
at  controls  of  Cyclotron 


Ernest  0.  Lawrence,  1901-1958.  Inventor  of  the  cyclotron,  with  which  he 
and  his  collaborators  have  investigated  the  structure  of  atoms,  produced 
artificial  radioactivity,  effected  transmutations  of  certain  elements,  and 
applied  artificial  radioactive  elements  to  the  study  of  biological  and  medical 
problems.  In  1939  he  was  awarded  the  Nobel  Prize  for  Physics.  Glenn  T. 
Seaborg,  1912-  .  Professor  of  chemistry  at  the  University  of  California. 
Codisooverer  of  element  94,  plutonium,  and  its  fissionable  isotope,  and  later 
of  elements  95  (americium)  and  96  (curium).  At  the  "Metallurgical 
Laboratory"  at  the  University  of  Chicago  he  had  charge  of  the  ultramicro- 
chemical  research  for  working  out  methods  for  the  separation  and  manu- 
facture of  plutonium  which  were  later  used  on  a  large  scale  at  Hanford, 
Washington,  and  Clinton,  Tennessee.  J.  Robert  Oppenheimer,  1904-  . 
Director  of  the  laboratories  at  Los  Alamos,  New  Mexico,  where  American 
and  European  scientists  worked  secretly  to  produce  the  first  atomic  bombs. 
Director  of  the  Institute  for  Advanced  Study  at  Princeton,  New  Jersey. 


31 

Elements  discovered  by  atomic  bombardment 


All  methods  tried  by  1937  had  failed  to  reveal  elements  number 
43,  61,  85  and  87,  and  no  element  was  known  beyond  uranium, 
number  92.  Then  came  the  discovery  of  the  cyclotron  and  later 
the  atomic  pile.  With  these  it  was  possible  to  bombard  ele- 
ments with  positive  particles  or  neutrons  to  create  new  elements. 
Soon  after  this  work  was  begun  the  empty  spaces  of  the  periodic 
table  were  filed.  Only  element  number  87,  francium,  discovered 
by  Mile.  Perey,  was  found  among  natural  decay  products  of 
actinium  without  help  of  atomic  bombardment.  This  powerful 
method  was  needed  for  Perrier  and  Segre  to  discover  technetium, 
Marinsky  and  Glendenin  to  find  promethium,  and  Segre,  Mac- 
kenzie, and  Corson  to  prepare  astatine.  The  table  was  appar- 
ently complete,  but  this  was  not  the  end.  In  1940  McMillan 
and  Abelson  obtained  the  first  transuranium  element,  neptunium. 
Under  the  stimulus  of  the  atomic  bomb  project  Seaborg  and  his 
group  synthesized  plutonium  and  guided  its  preparation  in  large 
amounts.  They  went  on  to  obtain  americium  and  curium.  After 
the  war  their  work  was  continued  at  the  University  of  California. 
Berkelium  and  californium  were  announced  in  1950,  elements 
99  and  100  in  1954,  and  element  101,  mendelevium,  in  1955. 

T 

JL  he  discovery  by  Frederic  and  Irene  Joliot-Curie*  of  artificial 
radioactivity  induced  by  neutron  bombardment  opened  the  way  for 
completion  of  the  periodic  table.  Spaces  still  remained  for  elements 
number  43,  61,  85,  and  87  before  the  apparent  end  was  reached  with 
uranium,  number  92.  Although  a  number  of  investigators  believed  that 
they  had  found  one  or  more  of  the  missing  elements,  and  several  had  even 
proposed  names  for  them,  positive  proof  of  their  existence  was  lacking. 
On  theoretical  grounds  it  was  suggested  that  these  elements  might  not 
exist  in  nature  in  amounts  sufficient  for  their  identification  even  by  such 
delicate  means  as  spectrum  analysis.  It  would  be  expected  that  these 
substances  might  be  radioactive,  and  so  might  have  disappeared  from 
the  earth  even  if  they  had  once  been  present  on  it.  Now,  however,  came 


This  chapter  was  written  by  Dr.  Henry  M.  Leicester. 
*  See  Chapter  29. 


859 


860  DISCOVERY  OF  THE  ELEMENTS 

the  possibility  of  creating  them  anew,  and,  what  was  even  more  exciting, 
of  preparing  elements  with  atomic  numbers  greater  than  92,  the  so- 
called  transuraniums. 

Experimental  studies  soon  confirmed  all  these  expectations.  The 
most  powerful  tool  in  achieving  these  results  was  the  cyclotron.  Ernest 
O.  Lawrence,  its  inventor,  was  born  in  Canton,  South  Dakota,  on  August 
8,  1901.  He  was  educated  at  St.  Olaf  College  and  the  University  of 
South  Dakota,  and  did  graduate  work  in  physics  at  Minnesota,  Chicago, 
and  Yale.  The  latter  university  gave  him  his  doctorate  in  1925.  He 
remained  at  Yale  until  1928,  and  was  then  called  to  the  University  of 
California  at  Berkeley,  where  he  still  remains  as  Director  of  the  Radiation 
Laboratory.  He  received  the  Nobel  Prize  in  Physics  in  1939.  It  was  due 
to  Lawrence  and  the  cyclotron  that  California  became  the  outstanding 
center  for  the  synthesis  of  new  elements,  which  it  still  remains  (1). 

In  1929,  while  glancing  through  a  German  periodical,  Lawrence 
noticed  a  diagram  of  an  apparatus  for  the  multiple  acceleration  of  positive 
ions  by  applying  radiofrequency  oscillating  voltages  to  a  series  of  cylindri- 
cal electrodes  in  line.  Almost  at  once  he  thought  of  modifying  this  idea 
by  circulating  the  positive  particles  back  and  forth  through  the  electrodes 
in  a  magnetic  field.  The  first  crude  cyclotron  based  on  this  idea  was 
constructed  by  Lawrence's  student,  Nils  Edlefsen,  in  1930.  From  this 
the  development  was  steady  up  to  the  enormously  powerful  bevatron 
now  in  operation  at  Berkeley  (2) .  This  apparatus  is  capable  of  furnishing 
tremendous  amounts  of  energy  either  directly,  in  the  form  of  positive 
particles  such  as  deuterons  or  helium  ions,  or  of  directing  these  onto 
suitable  targets  such  as  beryllium  to  produce  equally  powerful  beams  of 
neutrons.  Almost  all  the  elements  discussed  in  this  chapter  were  ob- 
tained from  such  beams. 

The  quantity  of  any  given  element  which  could  be  synthesized  in  the 
cyclotron  was  not  great.  In  most  cases  only  unweighable  amounts  of  the 
new  substances  were  obtained  in  it.  Specialized  techniques  had  to  be 
developed  to  identify  the  traces  of  the  elements  by  carrying  them  through 
a  series  of  reactions  with  elements  which  they  resembled  chemically. 
This  tracer  technique  has  yielded  a  surprising  amount  of  information  as 
to  the  chemistry  of  the  new  elements,  and  has  made  possible  the  positive 
identification  of  substances  which  are  present  in  amounts  too  small  even 
to  give  an  X-ray  spectrum. 

The  discovery  of  uranium  fission  by  Enrico  Fermi  and  L.  Szilard  at 
Columbia  University  opened  the  way  for  further  advances.  This  work 
was  done  under  the  cloak  of  wartime  secrecy  and  led  directly  to  the 
atomic  bomb,  but  its  significance  for  the  discovery  of  new  elements  was 
very  great. 

Fermi  was  born  in  Rome  on  September  29,   1901.     He  took  his 


ELEMENTS   DISCOVERED   BY   ATOMIC  BOMBARDMENT 


861 


Enrico  Fermi,  1901-1954.  Natu- 
ralized Italian-American  physicist. 
Professor  of  physics  at  Columbia 
University  and  the  University  of 
Chicago.  In  1938  he  was  awarded 
the  Nobel  Prize  for  Physics  in 
recognition  of  his  work  on  artificial 
radioactivity  induced  by  bombard- 
ment with  neutrons.  He  found 
that  the  effectiveness  of  neutron 
bombardment  is  much  greater  in 
presence  of  water  or  paraffin  and 
concluded  that  the  neutrons  are 
slowed  down  by  collisions  with  the 
hydrogen  nuclei  in  these  substances 
and  therefore  have  a  greater  prob- 
ability of  disrupting  nuclei.  The 
citation  accompanying  his  Congres- 
sional Medal  for  Merit,  awarded  in 
1946,  states  that  he  was  "the  first 
man  in  all  the  world  to  achieve 
nuclear  chain  reaction." 


Courtesy  Chemical  and  Engineering  News 


doctor's  degree  at  the  University  of  Pisa  in  1922  and  then  studied  with 
Max  Born  at  Gottingen  and  at  Leiden.  In  1924  he  returned  to  Italy,  to 
the  University  of  Florence,  and  in  1927  he  became  professor  of  theoretical 
physics  at  Rome.  In  1939  he  came  to  Columbia  University  and  began 
work  on  the  atomic  pile.  After  the  war  he  was  named  professor  of  physics 
at  the  University  of  Chicago.  He  was  awarded  the  Nobel  Prize  in  Physics 
in  1938.  He  died  at  the  height  of  his  career  in  1954  (3). 

The  operation  of  the  atomic  pile  is  based  on  the  fact  that  natural 
uranium,  chiefly  the  isotope  U238,  contains  some  U235  which  under  the 
impact  of  neutrons  undergoes  fission  to  produce  a  number  of  lighter 
elements  and  also  neutrons.  These  neutrons  can  be  slowed  down  in  their 
paths  by  graphite.  If  pieces  of  uranium  are  distributed  in  a  more  or  less 
regular  arrangement  through  a  graphite  lattice,  the  slowed  neutrons  can 
be  captured  by  the  U238  and  new  and  higher  elements  can  be  formed. 
The  atomic  pile  is  a  source  of  many  of  these  (4).  Because  of  the  large 
scale  on  which  the  piles  were  built  in  the  manufacture  of  the  atomic  bomb, 
relatively  large  supplies  of  the  new  substances  could  be  obtained.  Thus 
the  cyclotron  served  as  a  source  in  which  new  elements  could  first  be 
prepared  and  identified,  and  the  pile  then  furnished  them  in  amounts 
which  could  be  used  for  detailed  study.  The  combination  of  these  meth- 
ods has  been  responsible  for  striking  advances  in  the  last  decade. 


862  DISCOVERY  OF  THE  ELEMENTS 

TECHNETIUM 

Following  the  recognition  that  two  vacant  spaces  existed  in  the 
manganese  column  of  the  periodic  table,  a  number  of  attempts  were  made 
to  isolate  the  eka-  and  dvi-manganese.  Various  workers  believed  they  had 
succeeded  in  isolating  eka-manganese,  and  such  names  as  davyum, 
illmenium,  lucium,  and  nipponium  were  suggested  (5).  None  of  these 
claims  was  confirmed.  With  the  discovery  of  atomic  numbers  it  was 
recognized  that  eka-manganese  was  number  43.  In  1925  Noddack,  Tacke, 
and  Berg  at  the  time  they  described  the  properties  of  rhenium  ( Chapter 
30)  also  claimed  to  have  isolated  number  43,  which  they  named  masurium. 
In  spite  of  a  great  deal  of  work,  and  of  the  isolation  of  rhenium  in  large 
amounts,  the  existence  of  masurium  was  never  positively  established. 

Work  on  this  element  was  then  begun  by  Emilio  Gino  Segre  in 
Italy.  Segre  was  born  at  Tivoli,  Italy,  in  1905.  He  took  his  doctorate  in 
Rome  in  1928  and  remained  there  until  1935.  At  that  time  he  was  named 
professor  of  physics  at  the  Royal  University  of  Palermo,  where  he 
remained  until  1938.  He  then  came  to  the  Radiation  Laboratory  of  the 
University  of  California  at  Berkeley,  where  he  remained,  except  for  the 
years  from  1943  to  1945,  which  he  spent  at  Los  Alamos.  He  is  now  pro- 
fessor of  physics  at  the  University  of  California. 

In  December,  1936,  Ernest  Lawrence  sent  to  Segre  and  C.  Perrier  at 
Palermo  a  sample  of  molybdenum  which  had  been  bombarded  in  the 
cyclotron  for  several  months  with  a  strong  deuteron  beam.  The  sample 
showed  considerable  radioactivity.  Perrier  and  Segre  found  that  the 
activity  was  not  due  to  niobium,  zirconium,  or  molybdenum,  but  it  did 
accompany  carrier  samples  of  manganese  and  rhenium,  in  chemical 
separations.  The  active  material  resembled  rhenium  more  closely  in  its 
properties  than  it  did  manganese.  It  could  be  separated  from  its  carrier 
only  by  volatilization  in  a  current  of  hydrochloric  acid  (6).  Later  these 
investigators  found  that  it  could  be  extracted  by  boiling^  the  bombarded 
molybdenum  with  ammonium  hydroxide  containing  a  little  hydrogen 
peroxide  (7). 

All  the  preliminary  studies  on  the  chemical  properties  of  element  43 
were  conducted  with  unweighable  amounts  of  material.  Segre  estimated 
that  the  amount  they  used  was  about  10~10  gram  (8).  In  1940  Segre  and 
C.  S.  Wu  (9)  found  element  43  among  the  fission  products  of  uranium. 
Much  larger  amounts  were  obtained  from  this  source. 

In  1947  F.  A.  Paneth  (10)  pointed  out  that  there  was  no  justification 
in  considering  artificially  prepared  elements  as  different  from  those  which 
occurred  naturally.  He  therefore  laid  down  the  rule  that  the  discoverers 
of  such  elements  had  the  same  right  to  name  them  as  did  the  discoverers 
of  any  element.  Perrier  and  Segre  at  once  proposed  the  name  technetium, 


ELEMENTS   DISCOVERED   BY   ATOMIC   BOMBARDMENT  863 

symbol  Tc,  for  element  43,  deriving  the  name  from  the  Greek  word  for 
"artificial"  (11). 

The  reaction  of  formation  of  technetium  by  the  original  process  was 

42MoA  +  aH2  =  43TcA  +  on1. 

Subsequently  is  was  prepared  by  bombardment  of  molybdenum  by 
neutrons,  and  of  niobium  with  helium  -ions,  as  well  as  by  uranium 
fission  (5). 

When  larger  amounts  of  technetium  became  available,  studies  of  its 
chemical  properties  became  easier.  Pertechnate  salts  of  tetraphenylarsonic 
acid  were  found  to  be  useful  for  its  separation  (12).  At  the  Oak  Ridge 
Laboratory,  weighable  amounts  were  obtained  by  co-precipitating  the 
pertechnate  with  tetraphenyl  arsonium  perchlorate  and  electrolyzing  the 
homogeneous  solution  of  the  mixture  in  sulfuric  acid.  The  black  solid 
which  was  deposited  was  dissolved  in  a  mixture  of  nitric,  perchloric,  and 
sulfuric  acids.  The  technetium  was  co-distilled  with  perchloric  acid  and 
collected  under  dilute  ammonium  hydroxide.  Tc2ST  was  precipitated 
with  hydrogen  sulfide  and  dissolved  in  ammoniacal  hydrogen  peroxide. 
Evaporation  to  dryness  gave  a  mixture  of  NH4TcO4  and  (NHU^SCX 
which  was  reduced  by  hydrogen  to  give  0.6  gram  of  spectroscopically 
pure  technetium  metal  as  a  silver  gray,  spongy  mass  which  tarnished 
slowly  in  moist  air  (13).  It  burned  in  air  to  give  pure  Tc2O7.  When 
this  was  dissolved  in  water  and  the  solution  evaporated,  long,  red-black, 
hygroscopic  crystals  of  Tc2O7  H2O,  or  HTcO4>  were  formed  (14). 

PROMETHIUM 

The  properties  of  the  rare  earths  were  so  similar,  and  the  various 
discoveries  of  new  elements  in  this  group  so  confusing  (Chapter  26), 
that  no  one  could  be  sure  of  how  many  such  elements  actually  existed 
until  Moseley  derived  the  rules  for  determining  atomic  numbers.  It  was 
then  seen  that  one  rare  earth  remained  undiscovered,  occupying  the  place 
of  number  61,  between  neodymium  and  samarium.  Fractionation  of 
concentrates  of  these  elements  from  monazite  sands  by  J.  A.  Harris  and 
B.  S.  Hopkins  in  1926  (15)  gave  a  preparation  in  which  they  believed  they 
found  spectral  lines  of  element  61.  They  named  this  "illinium."  The 
announcement  was  promptly  challenged  by  L.  Rolla  and  L.  Fernandes 
of  the  Royal  University  of  Florence,  who  had  deposited  a  sealed  packet 
with  the  Accademia  dei  Lincei  in  1924.  In  this  they  had  described  a 
rare  earth  concentrate  which  they  believed  contained  element  61.  They 
gave  it  the  name  "florentium"  (16).  None  of  the  work  of  either  group 
was  successfully  repeated,  though  many  polemics  on  the  subject  appeared 
in  the  literature  in  the  next  few  years.  Other  groups  also  claimed  to  have 


864  DISCOVERY  OF  THE  ELEMENTS 

isolated  the  element,  but  with  no  more  success  than  their  predecessors. 
Hopkins  himself  suggested  that  the  element  might  be  radioactive  and 
short-lived  (17). 

When  the  cyclotron  bombardment  method  became  available,  H.  B. 
Law,  M.  L.  Pool,  J.  D.  Kurbatov,  and  L.  L.  Quill  at  Ohio  State  University 
bombarded  samples  of  neodymium  and  samarium  and  obtained  radio- 
active preparations  which  they  believed  might  contain  some  61  (IS). 
C.  S.  Wu  and  E.  Segre  confirmed  this  (19).  F.  A.  Paneth  pointed  out  that 
they  probably  actually  had  obtained  61  in  their  mixtures,  but  the  cyclo- 
tron method  was  not  sufficiently  powerful  to  give  conclusive  evidence 
of  its  existence  (10).  Nevertheless,  the  Ohio  State  group  proposed  the 
name  "cyclonium"  for  the  element. 


Charles  D.  Coryell,  1912-  .  Professor 
of  chemistry  at  the  Massachusetts  Insti- 
tute of  Technology.  Consultant  to  the 
Brookhaven  and  Oak  Ridge  National 
Laboratories  of  the  United  States  Atomic 
Energy  Commission.  The  studies  of  J.  A. 
Marinsky  and  L.  E.  Glendenin  in  his 
group  led  to  the  chemical  identification 
of  the  missing  element  61,  which  in  1949 
was  officially  named  promethium.  Dr. 
Coryell  participates  actively  in  the  scien- 
tific efforts  of  the  Federation  of  American 
Scientists  and  of  the  United  World  Fed- 
eralists toward  peace  and  world  stability. 


Courtesy  Record  of   Chemical  Progress 


The  final  answer  came  from  the  atomic  pile.  J.  A.  Marinsky,  L.  E. 
Glendenin,  and  C.  D.  Coryell  at  the  Clinton  Laboratories  at  Oak  Ridge 
(20)  obtained  a  mixture  of  fission  products  of  uranium  which  contained 
isotopes  of  yttrium  and  the  entire  group  of  rare  earths  from  lanthanum 
through  europium.  Using  a  method  of  ion-exchange  on  Amberlite  resin 
worked  out  by  E.  R.  Tompkins,  J.  X.  Khym,  and  W.  E.  Cohn  (21)  they 
were  able  to  obtain  a  mixture  of  praseodymium,  neodymium,  and  element 
61,  and  to  separate  the  latter  by  fractional  elution  from  the  Amberlite 
column  with  5  per  cent  ammonium  citrate  at  pH  2.75.  Neutron  irradia- 
tion of  neodymium  also  produced  61. 

Since  they  could  find  no  convincing  evidence  that  61  had  ever  been 


ELEMENTS   DISCOVERED   BY    ATOMIC   BOMBARDMENT  865 

detected  in  nature,  Marinsky  and  Glendenin,  having  isolated  the  element 
in  milligram  amounts,  claimed  its  discovery  and  named  it  prometheum, 
symbol  Pm,  after  the  Titan  in  Greek  mythology  who  stole  fire  from 
heaven  for  the  use  of  mankind.  The  name  was  suggested  to  them  by 
Grace  Mary  Coryell  (22}.  They  pointed  out  that  the  name  not  only 
symbolized  the  dramatic  method  of  producing  the  metal  by  harnessing 
the  energy  of  nuclear  fission,  but  also  warned  of  the  impending  danger  of 
punishment  by  the  vulture  of  war.  Their  claim  was  accepted  by  the 
International  Union  of  Chemistry  in  1949,  but  the  spelling  was  changed 
to  promethium  to  make  the  name  conform  to  those  of  other  metals  (23). 
One  study  has  been  made  on  the  biological  effects  of  promethium.  Its 
injection  results  in  its  localization  on  the  surfaces  of  bones,  from  which 
it  is  removed  extremely  slowly  (24). 

ASTATINE 

Search  for  the  missing  halogen,  eka-iodine,  was  actively  pursued  for 
many  years.  One  of  the  most  widely  publicized  claims  for  its  discovery 
was  that  of  F.  Allison  who  developed  a  magneto-optical  method  by  which 
he  believed  he  had  identified  the  element.  He  named  it  "alabamine" 
(25).  The  claim  was  not  subsequently  verified,  and  the  element  was 
actually  found  only  after  use  of  the  cyclotron  began. 

In  1940  D.  R.  Corson,  K.  R.  Mackenzie,  and  E.  Segre  at  the  University 
of  California  bombarded  bismuth  with  alpha  particles  (26,  27).  Pre- 
liminary tracer  studies  indicated  that  they  had  obtained  element  85, 
which  appeared  to  possess  metallic  properties.  The  pressure  of  war  work 
prevented  a  continuation  of  these  studies  at  the  time.  After  the  war,  the 
investigators  resumed  their  work,  and  in  1947  proposed  the  name  astatine, 
symbol  At,  for  their  element.  The  name  comes  from  the  Greek  word  for 
"unstable,"  since  this  element  is  the  only  halogen  without  stable  isotopes 
(28).  The  longest  lived  isotope  is  At210  with  a  half-life  of  8.3  hours  and  a 
very  high  activity. 

Tracer  studies  of  the  chemical  properties  showed  that  astatine  was 
soluble  in  organic  solvents,  could  be  reduced  to  the  —1  state,  and  had  at 
least  two  positive  oxidation  states.  These  studies  were  made  on  solutions 
of  10"11  to  10~15  molar  astatine  (29).  The  similarity  between  astatine  and 
iodine  was  found  to  be  less  close  than  that  between  technetium  and 
rhenium  or  that  between  promethium  and  the  other  rare  earths  (30). 

Like  iodine,  astatine  tends  to  accumulate  in  the  thyroid  gland  of  the 
living  animal  (31).  The  radioactivity  of  the  element  thus  concentrated 
seems  to  cause  severe  damage  to  thyroid  tissue  without  affecting  the 
adjacent  parathyroid  glands.  It  may  therefore  be  useful  in  cases  of 
hyperthyroidism  (32) .  Therefore  it  is  important  to  determine  the  amount 


866  DISCOVERY  OF  THE  ELEMENTS 

of  astatine  in  living  tissue.  This  can  be  done  by  perchloric-nitric  acid 
digestion  of  the  organic  matter.  No  loss  of  astatine  occurs  during  this 
digestion.  The  astatine  can  then  be  co-precipitated  with  metallic 
tellurium  or  deposited  on  silver  foil  (33).  Thus,  an  element  which  does 
not  occur  in  nature,  and  which  can  be  obtained  only  in  unweighable 
amounts,  may  still  have  important  therapeutic  uses. 

FRANCIUM 

As  in  the  case  of  astatine,  many  attempts  were  made  to  isolate  the 
heaviest  alkali  metal,  eka-cesium.  The  various  names  suggested  by  those 
who  believed  that  they  had  isolated  the  element  indicate  the  amount  of 
work  in  various  countries  which  was  done  in  this  field.  These  include 
russium,  alcalinium,  virginium,  and  moldavium  (34).  In  no  case  were 
these  claims  confirmed. 

The  actual  discovery  was  made  by  Mile.  Marguerite  Perey  at  the 
Curie  Institute  in  Paris.  In  1939  she  purified  an  actinium  preparation  by 
removing  all  the  known  decay  products  of  this  element.  In  her  prepara- 
tion she  observed  a  rapid  rise  in  beta  activity  which  could  not  be  due  to 
any  known  substance.  She  was  able  to  show  that,  while  most  of  the 
actinium  formed  radioactinium,  an  isotope  of  thorium,  by  beta  emission, 
1.2  ±  0.1  per  cent  of  the  disintegration  of  actinium  occurred  by  alpha 
emission  and  gave  rise  to  a  new  element,  which  she  provisionally  called 
actinium  K,  symbol  AcK  (35,  36) .  This  decayed  rapidly  by  beta  emission 
to  produce  AcX,  an  isotope  of  radium,  which  was  also  formed  by  alpha 
emission  from  radioactinium.  Thus  AcK,  with  its  short  half-life,  had 
been  missed  previously  because  its  disintegration  gave  the  same  product 
as  that  from  the  more  plentiful  radioactinium. 

Mile.  Perey  was  able  to  purify  AcK  by  dissolving  an  actiniferous 
lanthanum  ore  in  hydrochloric  acid  and  treating  the  solution  with  a 
slight  excess  of  sodium  carbonate  to  precipitate  most  of  the  contaminants, 
followed  by  a  little  barium  chloride  to  remove  all  AcX.  This  left  a 
solution  containing  only  AcK  and  AcC",  an  isotope  of  thallium.  The 
latter  disintegrates  faster  than  AcK,  but  if  its  chemical  removal  was 
desired,  it  could  be  precipitated  by  NH4HSO4,  tartrates,  or  chromates. 
The  AcK  could  then  be  co-precipitated  with  cesium  perchlorate,  or 
various  cesium  double  salts  (37).  It  was  later  shown  that  the  element 
could  also  be  co-precipitated  with  silicotungstic  acid  (38)  or  separated 
from  most  of  its  contaminants  by  paper  chromatography  (39). 

The  properties  of  this  new  element  left  no  doubt  that  it  was  the 
missing  alkali,  eka-cesium,  number  87.  In  1946  Mile.  Perey  suggested 
that  the  name  actinium  K  be  kept  for  the  naturally  occurring  isotope 
which  resulted  from  the  decay  of  actinium,  but  that  element  87  in  general 


ELEMENTS   DISCOVERED   BY   ATOMIC   BOMBARDMENT 


867 


be  called  francium,  symbol  Fa,  from  the  name  of  her  native  France 
(34,  40}.  The  name  was  accepted,  though  her  suggested  symbol  was 
changed  to  Fr  (41). 

The  failure  to  discover  francium  earlier  is  easy  to  understand  when 
it  is  remembered  that  the  half-life  of  the  longest  lived  isotope  is  only  21 
minutes.  This  gives  the  element  the  distinction  of  being  the  most  unstable 
to  radioactive  disintegration  of  all  elements  up  to  number  98  ( 38 ) .  It  is 
also  noteworthy  that  this  is  the  only  element  in  the  group  discussed  in 
this  chapter  which  was  not  discovered  by  artificial  preparation  in  the 
laboratory.  Nevertheless,  the  rarity  of  actinium  in  nature  is  so  great 
that  this  element  is  best  prepared  artificially  when  its  properties  or  those 
of  its  daughter  elements  are  to  be  studied. 

Mile.  Perey  has  recently  shown  that  when  francium  is  injected  into 
rats,  it  is  found  in  greatest  concentration  in  the  excretory  organs,  the 
kidneys,  saliva,  and  liver  (42).  In  rats  suffering  from  sarcoma,  the 
francium  activity  was  higher  in  the  tumor  tissue  than  in  normal  muscular 
tissue  (43).  Thus  the  element  may  eventually  have  medicinal  uses. 

THE  TRANSURANIUM  ELEMENTS 

In  1934,  Fermi  (44)  found  that  when  uranium  was  bombarded  with 
neutrons,  it  showed  evidence  of  neutron  capture  and  the  production  of 


Otto  Hahn,  1879-  .  President  of  the 
Max  Planck  Society  for  the  Promotion  of 
Science.  Discoverer  with  F.  Strassmann, 
in  1938,  of  the  splitting  of  uranium  and 
of  thorium  by  neutron  irradiation  into 
two  elements  of  medium  weight.  Dis- 
coverer of  radioactinium,  radiothorium, 
mesothorium,  uranium  Z,  and  (with  Miss 
Lise  Meitner)  protactinium.  He  has  de- 
vised radioactive  methods  for  determining 
the  geologic  and  biologic  age  of  mate- 
rials. In  1945  he  received  the  Nobel 
Prize  for  Chemistry  for  the  year  1944. 


Courtesy  Chemical  and  Engineering  News 


868  DISCOVERY  OF  THE  ELEMENTS 

artificial  radioactivity.  Fermi  and  his  co-workers,  knowing  that  beta 
emission  produces  an  element  of  higher  atomic  number  than  its  parent, 
expected  to  find  element  number  93  among  the  radioactive  products  of 
uranium  bombardment.  They  expected  the  transuranium  elements  in 
general  to  have  properties  similar  to  the  elements  below  them  in  the 
periodic  table,  such  as  rhenium,  osmium,  and  so  on.  When  they  did  not 
find  any  elements  with  atomic  numbers  from  86  to  92  in  their  products, 
they  believed  they  had  synthesized  elements  beyond  uranium.  This 
view  prevailed  for  several  years,  but  as  further  experiments  were  per- 
formed, it  became  less  and  less 'probable.  In  1939  O.  Hahn  and  F. 
Strassmann  (45)  discovered  that  under  these  conditions,  fission  was 
occurring,  and  the  products  of  neutron  bombardment  of  uranium  were 
elements  of  approximately  half  its  atomic  number  (46). 

NEPTUNIUM 

Among  the  fission  products  of  uranium,  one  unidentified  substance 
remained.  O.  Hahn,  Lise  Meitner,  and  F.  Strassmann  (47)  had  found 
a  substance  with  a  half-life  of  23  minutes  which  they  considered  an 
isotope  U235.  In  1940  Edwin  McMillan  at  the  University  of  California 
in  Berkeley,  while  investigating  the  properties  of  this  isotope,  discovered 
another  substance  associated  with  it  which  had  a  half -life  of  2.3  days. 
He  at  once  suspected  that  this  might  be  the  element  with  atomic  number 
93.  A  chemical  study  of  the  substance  was  made  by  E.  Segre  (48) .  This 
showed  that  the  substance  did  not  have  properties  similar  to  those  of 
rhenium,  as  was  expected  of  93.  Rather,  the  substance  resembled  the 
rare  earths.  In  spite  of  this,  McMillan  did  not  lose  interest  in  this  material. 

Edwin  M.  McMillan  was  born  on  September  18,  1907,  in  Redondo 
Beach,  California,  He  graduated  from  the  California  Institute  of  Tech- 
nology in  Pasadena  and  took  his  doctorate  in  physics  at  Princeton  Univer- 
sity in  1932.  He  then  went  to  Berkeley  as  a  National  Research  Fellow 
and  has  remained  on  the  faculty  there  ever  since,  except  for  a  period  of 
war  research  from  1940  to  1945.  He  received  the  Nobel  Prize  in  Chemis- 
try jointly  with  Seaborg  in  1951  (49,  50). 

In  the  spring  of  1940  Philip  Abelson  came  to  Berkeley  for  a  short 
vacation.  He  had  been  a  graduate  student  in  the  Radiation  Laboratory 
at  the  time  when  fission  was  announced,  and  was  now  at  the  Carnegie 
Institution  of  Washington,  where,  unknown  to  McMillan,  he  had  also 
begun  to  work  on  the  2.3-day  substance.  When  McMillan  and  Abelson 
discovered  their  mutual  interest,  they  decided  to  work  together  on  the 
problem  (51).  They  soon  established  the  fact  that  the  substance  could 
exist  in  a  reduced  and  an  oxidized  state,  with  valences  of  four  and  six, 
like  uranium,  which  it  resembled  also  in  other  respects.  Using  these 


ELEMENTS   DISCOVERED   BY   ATOMIC   BOMBARDMENT  869 

properties,  McMillan  and  Abelson  were  able  to  demonstrate  that  they 
were  dealing  with  the  first  transuranium  element,  number  93  (52). 
McMillan  subsequently  decided  to  name  ii  neptunium,  symbol  Np,  since 
it  was  the  element  next  to  uranium,  just  as  the  planet  Neptune  was  next 
to  Uranus  (53). 

The  existence  of  this  element  was  later  confirmed  in  Germany  by 
K.  Starke  (54)  and  by  F.  Strassmann  and  O.  Hahn  (55).  At  this  point 
in  his  work,  however,  McMillan  left  Berkeley  to  undertake  war  research 
on  radar.  He  turned  the  investigation  of  the  new  element  over  to  his 
colleague,  Glenn  T.  Seaborg  (51). 

Seaborg  dnd  his  co-workers  continued  the  work  actively,  and  sent 
a  number  of  communications  to  the  Physical  Review  during  1940  and  1941, 
but  these  were  not  published  until  1946.  The  impending  war  threw  a 
curtain  of  secrecy  over  all  their  program.  Discovery  of  the  fission  of 
element  94  ( 56 )  had  much  to  do  with  this.  By  1942  the  full  impact  of  the 
Manhattan  Project  for  making  atomic  bombs  was  felt  and  the  various 
workers  scattered  to  laboratories  of  the  project  in  Chicago,  Los  Alamos, 
and  elsewhere.  They  continued  to  cooperate  closely  in  their  investiga- 
tions, however.  Nothing  was  known  to  the  public  of  the  feverish  activities 
under  way  in  all  these  institutions.  The  unknowing  even  expressed  regret 
that  such  a  promising  field  of  research  had  been  abandoned  (57). 

After  the  war  security  restrictions  were  gradually  lifted,  though  by 
no  means  all  the  information  which  was  obtained  has  been  released  even 
in  1955.  It  was  learned  in  1948  (58)  that  the  first  pure  compounds  of 
neptunium  had  been  prepared -in  June  and  July  of  1944.  Bombardment 
of  64  pounds  of  uranium  in  the  Berkeley  cyclotron  yielded  about  two 
parts  of  neptunium  per  billion  parts  of  uranium  by  weight.  In  addition 
the  atomic  pile  was  also  yielding  neptunium  by  this  time.  In  all,  45 
micrograms  of  Np237  were  obtained.  From  this  the  hydroxide  of  the 
lower  oxidation  state  was  prepared  and  ignited  to  give  NpO2-  This  was 
shown  by  its  diffraction  pattern  to  be  isomorphous  with  the  dioxides 
of  thorium,  uranium,  and  plutonium,  proving  the  tetravalent  state  of  the 
element.  The  oxide  was  converted  to  the  hexavalent  state  as  sodium 
neptunium  dioxytriacetate.  The  manipulation  of  these  minute  amounts 
of  material  required  special  techniques  which  will  be  discussed  under 
plutonium.  Neptunium  exists  in  the  oxidation  states  III,  IV,  V,  and  VI 
with  a  shift  in  stability  toward  the  lower  valences  (58,  59).  It  has  been 
prepared  as  a  silvery  metal  by  heating  the  trifluoride  to  1200°  in  the 
presence  of  barium  vapors.  The  metal  is  not  much  affected  by  air  (60). 

The  neptunium  isotope  first  prepared  by  McMillan  was  Np239,  but 
the  atomic  pile  yielded  larger  amounts  of  Np237  which  has  a  half -life  of 
2.25  X  106  years  and  a  relatively  low  specific  alpha-particle  activity,  only 
about  one  thousand  times  that  of  uranium.  This  isotope  can  be  handled 


870  DISCOVERY  OF  THE  ELEMENTS 

in  an  ordinary  laboratory  without  too  great  difficulty,  and  Seaborg  be- 
lieves that  it  may  some  day  be  used  sparingly  in  university  laboratory 
courses  in  qualitative  analysis  and  advanced  inorganic  chemistry  ( 61 ) . 

Neptunium  is  also  interesting  because  it  can  be  considered  the 
parent  of  the  so-called  "missing  disintegration  series."  Th232  begins  a 
series  in  which  the  masses  of  all  the  members  can  be  distinguished  by  a 
formula  4n,  where  n  is  an  integer.  U238  begins  a  (4n  +  2)  series  and 
U235  a  (4n  +  3)  series.  There  is  no  natural  (4n  +  1)  series,  but  Np237 
supplies  this  gap  (62). 

This  element  has  not  been  found  in  any  naturally  occurring  mineral 
but  Seaborg  believes  it  may  exist  in  minute  amounts  as  the  result  of 
neutron  bombardment  in  uranium  ores  (63) .  Neptunium  is  not  absorbed 
from  the  digestive  tract  of  animals,  but  when  it  is  injected  it  tends  to 
accumulate  in  the  bones.  Subsequent  loss  from  this  site  is  very  slow 
(64,65). 


PLUTONIUM 

When  McMillan  left  Berkeley  in  November  1940  he  turned  over 
his  transuranium  studies  to  Seaborg.  Glenn  Theodore  Seaborg  was  born 
on  April  19,  1912,  at  Ishpeming,  Michigan.  When  he  was  ten  his  family 
moved  to  Los  Angeles,  where  he  attended  school  and  graduated  in  1934 
trom  the  University  of  California  at  Los  Angeles.  He  then  went  to  the 
Berkeley  campus  of  the  University,  where  he  received  his  doctorate  in 
1937  with  a  thesis  on  the  inelastic  scattering  of  fast  neutrons.  He  joined 
the  faculty  at  Berkeley  in  1939.  From  1942  to  1946  he  was  chief  of  the 
section  on  transuranium  elements  at  the  Manhattan  Project  Metallurgical 
Laboratory  at  the  University  of  Chicago.  In  1946  he  returned  to 
Berkeley  and  has  since  carried  on  his  work  there.  He  and  McMillan 
shared  the  1951  Nobel  Prize  in  Chemistry  (50,  66). 

McMillan  had  been  sure  that  another  element  was  present  in  his 
neptunium  fractions.  In  December,  1940,  Seaborg,  A.  C.  Wahl,  and 
J.  W.  Kennedy  separated  from  neptunium  a  fraction  which  had  alpha 
activity  and  which  showed  at  least  two  oxidation  states.  It  required 
stronger  oxidizing  agents  to  oxidize  this  substance  than  were  needed  for 
neptunium.  The  new  element  was  identified  as  94.  The  notes  reporting 
this  discovery  were  submitted  to  the  journals  early  in  1941,  but  were  not 
published  until  1946  (67,  68). 

The  isotope  first  isolated  resulted  from  beta  emission  by  Np238.  In  the 
spring  of  1941  Seaborg's  group  isolated  a  new  isotope,  prepared  by 
neutron  bombardment  of  U238.  The  series  of  reactions  was : 


ELEMENTS   DISCOVERED   BY   ATOMIC   BOMBARDMENT  871 


Courtesy  Chemical  and  Engineering  News 


G.  T.  Seaborg  and  E.  M.  McMillan.  The  Nobel  Prize  for  Chemistry  for 
1951  was  awarded  jointly  to  Glenn  T.  Seaborg  and  Edwin  M.  McMillan, 
both  of  the  University  of  California,  for  "their  discoveries  in  the  chemistry 
of  the  transuranium  elements."  Dr.  Seaborg  is  chairman  of  the  Division 
of  Physical  and  Inorganic  Chemistry  at  the  University  of  California.  Dr. 
McMillan  worked  at  the  Massachusetts  Institute  of  Technology  in  connec- 
tion with  radar  development,  collaborated  with  J.  Robert  Oppenheimer 
in  organizing  the  Los  Alamos  Scientific  Laboratory,  and  did  the  initial  work 
that  led  to  the  discovery  of  elements  heavier  than  uranium. 


872  DISCOVERY  OF  THE  ELEMENTS 

P- 

U238  +  n  ->  U239  >  Np239  ->  Pu239 

decay 

This  isotope  had  a  half-life  of  about  24,000  years.  It  proved  to  be 
fissionable  (56)  and  was  the  basis  for  the  plutonium  atomic  bomb.  Con- 
centrated work  on  the  new  element  was  now  begun  by  the  Manhattan 
Project.  The  main  work  was  done  at  Chicago.  At  this  time  it  became 
desirable  to  have  names  for  the  elements  which  had  previously  been 
called  simply  93  and  94  by  the  men  who  worked  with  them.  The  name 
suggested  by  McMillan,  neptunium,  was  therefore  adopted  for  93,  and 
by  analogy  94  was  named  plutonium  from  the  planet  Pluto,  next  beyond 
Neptune  in  the  solar  system  (53,  69). 

It  is  interesting  that  this  name,  plutonium,  had  once  before  been 
suggested  for  an  element.  About  1817  Edward  Daniel  Clarke  (1769- 
1822),  professor  of  mineralogy  at  Cambridge  University,  suggested'  that 
this  name  be  used  instead  of  barium,  since  barium  metal  was  not  un- 
usually heavy.  He  suggested  this  name  because  barium,  isolated  by 
electrolysis,  "owed  its  existence  to  the  dominion  of  fire"  (70). 

All  the  early  work  on  plutonium  was  done  with  unweighable  amounts 
on  a  tracer  scale.  When  it  became  apparent  that  large  amounts  would 
be  needed  for  the  atomic  bomb,  it  was  necessary  to  have  a  more  detailed 
knowledge  of  the  chemical  properties  of  this  element.  Intensive  bombard- 
ment of  hundreds  of  pounds  of  uranium  was  therefore  begun  in  the 
cyclotrons  at  Berkeley  and  at  Washington  University  in  St.  Louis.  /Sepa- 
ration of  plutonium  from  neptunium  was  based  on  the  fact  that  neptunium 
is  oxidized  by  bromate  while  plutonium  is  not,  and  that  reduced  fluorides 
of  the  two  metals  are  carried  down  by  precipitation  of  rare  earth  fluorides, 
while  the  fluorides  of  the  oxidized  states  of  the  two  elements  are  not. 
Therefore  a  separation  results  by  repeated  bromate  oxidations  and 
precipitations  with  rare  earth  fluorides. 

This  work  was  carried  on  by  B.  B.  Cunningham  and  L.  B.  Werner. 
On  August  18,  1942,  they  isolated  about  one  microgram  of  a  pure  com- 
pound. This  was  the  first  sight  of  a  synthetic  element  and  the  first 
case  of  the  isolation  of  a  weighable  amount  of  an  artificially  produced 
isotope  (71,  59,  69).  In  September,  30  micrograms  of  the  element 
were  obtained  and  the  iodate,  hydroxide,  peroxide,  and  ammonium  pluto- 
nium fluoride  were  prepared  in  a  pure  state. 

The  work  had  now  progressed  from  the  tracer  to  the  microgram 
stage.  Normally,  this  stage  could  have  lasted  for  many  years.  At  this 
time,  however,  plans  were  being  made  for  the  construction  of  a  plant  to 
produce  plutonium  on  a  large  scale,  and  it  was  necessary  to  know  the 


ELEMENTS   DISCOVERED   BY   ATOMIC   BOMBARDMENT 


873 


behavior  of  plutonium  compounds  in  the  concentrations  which  would 
be  used  in  the  plant.  This  problem  was  brilliantly  solved  by  the  use  of 
ultramicrochemical  methods.  The  apparatus  used  was  so  small  that  all 
operations  had  to  be  carried  out  on  the  stage  of  a  microscope.  Actual 
chemical  reactions  were  conducted  with  micrograms  of  material  in  solu- 
tions with  volumes  on  the  order  of  10"1  to  10~5  ml.  They  soon  revealed 
much  of  the  chemistry  of  plutonium  (4,  71,  72).  The  information  ob- 
tained in  this  way  made  possible  the  almost  simultaneous  construction  of 
the  plutonium  plant  at  Hanford,  Washington,  a  step  up  of  1010-fold, 
"surely  the  greatest  scale  up  factor  ever  attempted,"  as  Seaborg  later 
said  (72).  Yet  this  scale  up  was  entirely  successful.  After  large  amounts 
of  plutonium  became  available,  ordinary  chemical  methods  could  be 
used,  but  because  of  the  extreme  radioactivity  of  the  element,  there  was 
the  further  complication  of  having  to  perform  all  manipulations  at  a 
distance  and  behind  shielded  walls.  Many  further  remarkable  devices 
were  designed  to  overcome  these  difficulties.  Radiochemistry  has  become 
a  highly  specialized  field. 

The  chemistry  of  plutonium  is  now  well  known.    It  has  valence  states 
of  III,  IV,  V,  and  VI  and  many  of  its  compounds  have  been  prepared 


A  nuclear  agent  caused  by  270-Mev  protons  accelerated  in  the  184-inch 
cyclotron  at  the  Radiation  Laboratory,  University  of  California.  A  neutron 
(leaving  no  trail  because  it  carries  no  electrical  charge)  strikes  an  emulsion 
atom  at  upper  left,  producing  a  negative  heavy  meson  and  two  heavier 
particles,  probably  protons.  The  meson  moves  to  the  right,  stopping  in 
another  emulsion  atom  and  giving  up  its  energy  by  knocking  out  another 
heavy  particle,  probably  an  alpha  particle. 


874  DISCOVERY  OF  THE  ELEMENTS 

(59,  73).  The  lower  oxidation  states  are  more  stable  than  those  of 
neptunium  (59).  Much  that  is  known  has  not  been  disclosed,  but  the 
information  is  slowly  emerging.  Thus,  only  in  1954  was  it  revealed  that 
the  metallurgists  at  Los  Alamos  in  1945  knew  that  plutonium  metal  had 
•the  unique  property  of  possessing  at  least  five  allotropic  modifications  at 
atmospheric  pressure  (74). 

Plutonium  is  the  only  transuranium  element  which  has  been  found 
in  nature.  Until  its  properties  were  known  it  would  have  been  impossible 
to  detect  it  in  the  minute  amounts  in  which  it  occurs,  but  when  its  be- 
havior was  understood,  Seaborg  and  his  co-workers  were  able  to  find  it  in 
pitchblende,  monazite  ores,  and  carnotite  in  concentrations  of  about  one 
part  in  1014  (63,  75,  76).  Peppard  and  his  group  found  it  in  somewhat 
greater  amounts  in  pitchblende  from  the  Belgian  Congo  (77).  Seaborg 
believes  that  most  of  this  plutonium  arises  by  fission  of  the  uranium  in  the 
ore,  though  other  processes  may  also  be  involved  (77,  78). 

Plutonium  is  not  readily  absorbed  from  the  animal  intestine  (65), 
though  on  long  continued  low-level  feeding  some  is  taken  up  ( 79 ) .  There 
is  some  absorption  through  the  lungs,  and  when  it  enters  the  body  by 
this  path  or  by  injection,  it  localizes  in  the  bones  (64,  65).  It  is  probably 
more  toxic  than  radium  under  these  conditions  (65).  It  is  not  actually 
incorporated  into  the  mineralized  matter  of  the  bone  as  is  radium,  but 
seems  to  concentrate  in  the  cartilaginous  portion  (24). 

AMERICIUM  AND  CURIUM 

\  One  of  the  characteristics  of  the  production  of  new  radioactive 
elements  is  that  each  new  one  which  is  found  at  once  opens  the  possi- 
bility of  advancing  one  place  in  the  periodic  table  if  beta  emission  occurs. 
Thus  there  is  always  a  higher  element  to  beckon  the  investigator  on. 
Added  to  this  is  the  fact  that  each  of  the  radioactive  elements  has  a  large 
number  of  isotopes,  and  that  there  are  various  types  of  particles  with 
which  these  isotopes  can  be  bombarded.  Besides  neutrons,  deuterons,  and 
helium  ions  which  have  been  mostly  used  up  to  the  present,  the  future 
holds  promise  of  the  use  of  still  larger  particles  such  as  ions  of  oxygen  or 
nitrogen.  Thus  the  number  of  possible  transuranium  elements  is  limited 
only  by  their  own  stability  and  by  the  possibility  of  their  chemical  or 
physical  identification.  f 

Since  this  is  so,  it  was  inevitable  that  as  soon  as  Seaborg  and  his 
collaborators  had  clearly  established  the  identity  and  properties  of 
neptunium  and  plutonium,  they  would  look  for  the  next  higher  elements, 
numbers  95  and  96.  The  general  similarity  in  chemical  properties  of 
uranium,  neptunium,  and  plutonium  led  Seaborg  to  believe  that  these 
new  elements  could  be  isolated  by  methods  similar  to  those  already  used. 


ELEMENTS    DISCOVERED    BY    ATOMIC    BOMBARDMENT  875 

In  the  summer  of  1944,  Seaborg  realized  that  in  the  transuranium  ele- 
ments he  was  dealing  with  a  group  resembling  the  rare  earths.  The 
higher  transuranium  elements  should  have  properties  similar  to  the 
heavier  rare  earths.  Thus  the  predominant  valence  should  be  three. 
When  these  ideas  were  applied  element  96  was  found  almost  at  once  in  a 
sample  of  Pu239  which  had  been  bombarded  with  helium  ions  in  the 
Berkeley  cyclotron.  In  the  late  fall  of  1944  element  95  was  found  as  a 
result  of  neutron  bombardment  of  Pu239.  For  nearly  a  year,  however, 
attempts  at  chemical  separation  and  identification  failed.  During  this 
period  the  elements  remained  unnamed,  though  'Seaborg  reports  that 
one  disgusted  member  of  his  group  insisted  on  referring  to  them  as 
"pandemonium"  and  "delirium"  (69).  Since  these  elements  resemble  the 
rare  earths  so  closely,  they  can  best  be  separated  by  the  very  efficient 
method  of  adsorption  on  cation  exchange  resins  and  selective  elution  with 
suitable  solvents.  This  method,  which  has  replaced  the  old,  tedious  frac- 
tional crystallizations  of  the  salts,  has  made  the  rare  earth  chemistry  much 
clearer  than  it  has  ever  been.  It  will  be  recalled  that  promethium  was 
isolated  by  this  procedure.  The  similarity  of  the  transuranium  elements 
to  the  rare  earths  extends  to  this  process  also,  and  it  is  so  accurate  that  the 
conditions  for  the  elution  of  a  given  substance  can  be  predicted  in 
advance  and  can  be  used  as  evidence  in  identifications  (SO). 

The  first  pure  compound  of  element  95  was  obtained  by  B.  B. 
Cunningham  in  the  fall  of  1945,  and  the  first  of  96  by  L.  B.  Werner  and 
I.  Perlman  at  Berkeley  in  the  fall  of  1947  (69).  The  elements  were  named 
by  analogy  with  the  corresponding  rare  earths.  Number  95,  the  analogue 
of  europium,  was  named  americium,  symbol  Am,  and  number  96,  the 
analogue  of  gadolinium  which  was  named  for  the  famous  investigator 
of  rare  earths  Johan  Gadolin,  was  named  for  the  investigators  of  radio- 
activity, the  Curies.  It  was  called  curium,  symbol  Cm.  Chemical  studies 
of  these  elements  have  been  difficult  because  of  their  intense  radioactivity. 
Curium  is  so  active  that  solutions  of  its  salts  decompose  water  (61,  SI). 
Nevertheless,  many  compounds  have  been  prepared,  and  the  pure 
metals  have  been  obtained  by  reduction  of  the  trifluorides  with  barium 
vapors  at  1100-1300°  in  a  vacuum.  Americium  is  a  silvery,  very  malleable 
and  ductile  metal  with  a  very  low  density,  a  property  also  possessed  by 
europium.  It  tarnishes  in  air  and  forms  a  hydride  with  hydrogen  (82). 
Curium  is  a  silvery  metal,  almost  as  malleable  as  plutonium,  but  more 
reactive  than  either  plutonium  or  americium,  since  it  tarnishes  even  in  dry 
nitrogen  (83). 

Americium  and  curium  injected  into  animals  are  distributed  to  the 
extent  of  about  25  per  cent  in  bone,  but  unlike  neptunium  and  plutonium, 
about  70  per  cent  of  the  injected  dose  is  found  in  the  liver.  Loss  from  the 


876  DISCOVERY  OF  THE  ELEMENTS 

latter  organ  occurs  fairly  soon  (64).     The  part  of  the  americium  that 
enters  bone  is  deposited  on  the  surfaces,  like  promethium  and  plutonium 

(24). 

THE  ACTINIDE  SERIES 

A  hypothesis  which  has  been  of  the  greatest  value  in  isolating  and 
identifying  the  transuranium  elements  was  set  forth  by  Seaborg  in  1944 
and  has  been  described  frequently  since  (69).  This  is  based  on  the 
analogy  of  the  transuraniums  with  the  rare  earths.  The  latter  group 
begins  with  lanthanum,  and  may  be  considered  a  group  of  lanthanides. 
The  analogue  of  lanthanum  is  actinium,  and  so  the  transuranium  elements 
can  be  considered  to  belong  to  an  actinide  group.  The  similarity  in 
chemical  properties  of  the  members  of  the  lanthanides  depends  upon  the 
fact  that  in  them  the  4d  electron  shell  is  being  progressively  filled  as  the 
series  advances.  In  the  actinides  it  is  the  5f  shell  which  is  filling.  The 
lanthanides  end  with  lutetium,  number  71.  The  actinides  should  end 
with  element  103.  The  actinide  theory  has  served  as  a  valuable  guide  in 
separating  the  members  of  this  series  (84,  85).  Some  chemists  have 
questioned  it  on  chemical  grounds,  since  the  properties  of  the  first  mem- 
bers of  the  series  up  to  plutonium  seem  to  differ  greatly  from  the  charac- 
teristic trivalent  compounds  of  the  lanthanides  ( 86,  87,  88 ) .  This  appears 
to  be  a  somewhat  formal  distinction,  however. 


BERKELIUM  AND  CALIFORNIUM 

Continuation  of  the  study  of  the  radioactive  elements  produced  by 
cyclotron  bombardment  of  lower  elements  led  in  1950  to  isolation  by 
tracer  techniques  of  numbers  97  and  98.  Bombardment  of  Am241  with 
helium  ions  by  S.  G.  Thompson,  A.  Ghiorso,  and  G.  T.  Seaborg  produced 
97243  wm*ch  resembled  its  analogue,  terbium,  in  its  elution  from  ion- 
exchange  resins.  Since  terbium  was  named  from  the  city  of  Ytterby,  97 
was  named  from  the  city  in  which  so  many  new  elements  had  been 
discovered,  Berkeley,  and  the  name  berkelium  and  symbol  Bk  have  been 
accepted  (89,  90). 

Helium  ion  bombardment  of  Cm242  by  S.  G.  Thompson,  K.  Street,  Jr., 
A.  Ghiorso,  and  G.  T.  Seaborg  produced  98244.  At  this  point  naming  by 
analogy  with  the  rare  earths  broke  down,  since  no  good  analogy  with  the 
name  dysprosium  was  available.  The  discoverers  therefore  chose  to 
honor  the  university  and  state  in  which  the  discovery  was  made,  and  the 
name  californium,  symbol  Cf,  was  chosen.  The  discoverers  remarked, 
however,  that  "the  best  we  can  do  is  to  point  out,  in  recognition  of  the 


ELEMENTS   DISCOVERED   BY   ATOMIC   BOMBARDMENT  877 

fact  that  dysprosium  is  named  on  the  basis  of  a  Greek  word  meaning 
"difficult  to  get  at/  that  the  searchers  for  another  element  a  century  ago 
found  it  difficult  to  get  to  California"  (91).  Only  a  few  thousand  atoms  of 
californium  were  isolated  in  any  of  the  experiments  on  this  element 
(92).  Tracer  experiments  have  indicated  a  predominant  trivalent  state 
for  both  berkelium  and  californium,  with  evidence  for  a  tetravalent  state 
in  the  former  and  less  clear  evidence  for  this  state  in  the  latter  (93,  94). 


Courtesy  Chemical  and  Engineering  News 

University  of  California  Bevatron.  A  section  of  the  giant  Bevatron  financed 
by  the  Atomic  Energy  Commission  at  the  University  of  California  Radiation 
Laboratory,  Berkeley.  At  far  right  is  the  Cockroft-Walton,  which  starts 
particles  on  their  300,000  mile  journey  through  the  machine.  The  large 
tube-shaped  instrument  at  right  center  is  the  linear  accelerator,  which  boosts 
particles  to  10  million  electron  volts.  At  left  is  the  giant  Bevatron  magnet  in 
which  particles  are  accelerated  to  cosmic  ray  energies. 


Shortly  after  the  announcement  of  the  naming  of  berkelium  A.  P. 
Znoiko  in  Russia,  who  had  made  earlier  predictions  of  the  properties  of 
element  97,  suggested  that  Mendeleev  should  be  honored  by  giving  his 
name  to  this  element,  calling  it  mendelevium  (95).  The  name  berkelium 
had  already  been  adopted,  but,  as  will  be  seen,  at  the  first  opportunity  the 
Berkeley  group  did  honor  the  father  of  the  periodic  table. 


878  DISCOVERY  OF  THE  ELEMENTS 

EINSTEINIUM,  FERMIUM,  MENDELEVIUM  AND  ELEMENT  102 
StiU  the  search  continued.  In  1954  several  laboratories  reported  the 
isolation  and  study  of  elements  99  and  10O.  A  group  at  Berkeley  gave 
some  details  of  the  discovery  of  99  (96),  and  soon  afterwards  ot  100  (97). 
Only  minute  amounts  of  these  substances  were  obtained,  but  the  elution 
sequences  on  ion-exchange  resins  served  to  identify  them.  Physical  prop- 
erties were  reported  from  both  Berkeley  (9«)  imd  the  Arfionne-  Labora- 
tories at  Arco,  Idaho  ( 99 ) .  The  authors  of  all  these  papers  added  notes  to 
their  reports  stating  that  unpublished  information  still  remained,  and 
that  no  attempt  should  be  made  to  prejudge  questions  of  priority  of 
discovery  on  the  basis  of  the  published  papers. 

The  reason  for  these  cautions  became  apparent  when  more  details 
could  be  given.  In  the  summer  of  1955  it  was  revealed  that  these  ele- 
ments had  actually  been  discovered  among  the  substances  produced  in 
uranium  which  had  been  subjected  to  a  very  high  instantaneous  neutron 
flux  in  the  thermonuclear  explosion  of  November,  1952.  Groups  at  the 
University  of  California,  the  Argonne  Laboratories,  and  the  Los  Alamos 
Laboratories  had  worked  simultaneously  on  the  identification  of  the  new 
elements  and  had  established  their  existence  and  elution  properties. 
Later  intense  neutron  irradiation  of  Pu239  confirmed  their  results.  Until 
the  secrecy  surrounding  the  thermonuclear  explosion  was  lifted,  only 
guarded  reports  of  this  work  could  be  given.  With  fuller  details  the 
investigators  suggested  the  names  einsteinium  (symbol  E)  for  element 
99  and  fermium  (symbol  Fm)  for  element  100.  Thus  the  fundamental 
studies  of  Albert  Einstein  and  Enrico  Fermi  will  be  perpetuated  (102). 

The  complexity  of  the  reactions  involved  in  the  bombardment  of 
plutonium  and  the  production  of  higher  transuranium  elements  can  be 
seen  from  the  following  scheme  which  indicates  the  method  of  synthesis  of 
einsteinium  and  fermium: 

Pu239  +  2n  -»  Pu241      g'    >  Am2"  -+-  n  ->  Am-'12  — — >  Cm-42 

doeuy 

.»  Bk~50  — 1— >  CFr»° 


decay 


Cf250  +  3n  -»  Cf253  — >E253  -j-  n  -»  E254 ->  Fm254  (100) 

decay  decay 

In  1955  the  next  step  was  announced.  Very  intense  helium  ion 
bombardment  of  tiny  targets  of  E253  produced  a  few  spontaneously  fission- 
able atoms  which  eluted  from  ion-exchange  resins  in  the  eka-thulium 
position.  This  was  evidence  that  element  101  had  been  found.  Only 
seventeen  atoms  of  this  element  were  produced.  It  showed  a  half -life  of 
between  one-half  and  several  hours.  The  name  mendelevium  (symbol 


ELEMENTS    DISCOVERED    BY    ATOMIC    BOMBAKDMENT  879 

Md)  was  proposed  by  the  discoverers,  A.  Ghiorso,  B.  G.  Harvey,  G.  R. 
Choppin,  S.  G.  Thompson,  and  G.  T.  Seaborg,  in  honor  of  the  basic  ideas 
of  D.  I.  Mendeleev  on  which  have  depended  all  discoveries  of  elements 
since  his  day  (100,  101). 

In  1957  a  group  of  scientists  at  the  Argonne  Laboratory,  the  Atomic 
Energy  Research  Establishment  at  Harwell,  England,  and  the  Nobel  In- 
stitute for  Physics  in  Stockholm  announced  the  isolation  of  element  102 
(103).  They  proposed  the  name  nobelium  for  this  element.  However, 
workers  at  the  University  of  California  Radiation  Laboratory  could  not 
confirm  this  claim  (104),  but  did  identify  the  isotope  102254  which  they 
obtained  by  bombardment  of  Cm246  with  C12  ions  in  the  linear  accelerator. 
They  did  not  immediately  propose  a  name  to  replace  the  name  nobelium 
(105). 

The  chemical  and  nuclear  properties  of  each  of  the  new  elements  is 
discussed  at  greater  length  in  the  January  1959  issue  of  Journal  of  Chemi- 
cal Education  (106), 

The  cooperation  of  Mr.  James  M.  Crowe,  Executive  Editor  of  Chemi- 
cal and  Engineering  News,  in  procuring  illustrations  for  this  chapter  is 
gratefully  acknowledged. 

LITERATURE  CITED 

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880  DISCOVERY  OF  THE  ELEMENTS 

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(57)  FOSTER,  L.  S.,  "Synthesis  of  the  new  elements  neDtunium  and  plutonium," 

J.  Chem.  Educ.,  22,  619-23  (1945). 

(58)  MAGNUSSON,  L.  B.  and  T.  J.  LACHAPELLE,  "The  first  isolation  of  element 

93  in  pure  compounds  and  a  determination  of  the  half  life  of  93Np237," 
J.  Am.  Chem.  Soc.,  70,  3534-8  ( 1948). 

(59)  SEABORG,   G.  T.,   "The  chemical  and  radioactive  properties  of  the  heavy 

elements,"  Chem.  Eng.  News,  23,  2190-3  (1945). 

(60)  HULL,  W.  Q.,  "The  transuranium  elements,"  Chem.  Eng.  News,  30,  232-7 

(1952). 

(61)  SEABORG,  G.  T.,  "Plutonium  and  the  other  transuranium  elements,"  Chem. 

Eng.  News,  25,  358-60  (1947). 

(62)  "Seaborg  tells  of  isotope  synthesis  at  Nichols  Medal  award,"  Chem.  Eng. 

News,  26,  740-1  (1948). 

(63)  LEVINE,  C.  A.  and  G.  T.  SEABORG,  "Occurrence  of  plutonium  in  nature," 

J.  Am.  Chem.  Soc.,  73,  3278-83  (1951). 

(64)  HAMILTON,  J.  G.,  "The  metabolism  of  the  fission  products  and  the  heaviest 

elements,"  Radiology,  49,  32S-43  (1947). 

(65)  HAMILTON,  J.  G.,  "Metabolism  of  radioactive  elements  created  by  nuclear 

fission,"  New  Engl  J.  Med.,  240,  863-70  (1949). 

(66)  "Glenn  Theodore  Seaborg,"  Les  Prix  Nobel  en  1951,  Imprimerie  Royale, 

Stockholm,  1952,  pp.  89-90. 


882  DISCOVERY  OF  THE  ELEMENTS 

(67)  SEABORG,  G.  T.,  E.  M.  MCMILLAN,  J.  W.  KENNEDY,  and  A.  C.  WAHL,  "Radio- 

active element  94  from  deuterons  on  uranium,"  Phys.  Rev.,  69,  366-7 
(1946).  (Article  originally  received  Jan.  28,  1941.) 

(68)  SEABORG,  G.  T.,  A.  C.  WAHL,  and  J.  W.  KENNEDY,  "A  new  element:    radio- 

active element  94  from  deuterons  on  uranium,"  Phys.  Rev.,  69,  367  ( 1946 ) . 
(Article  originally  received  March  7,  1941.) 

(69)  SEABORG,  G.  T.,  "The  transuranium  elements:     present  status,"  Les  Prix  Nobel 

en  1951,  Imprimerie  Royale,  Stockholm,  1952,  pp.  141-64. 

(70)  WEBB,  K.  R.,  "Naming  the  elements:    a  fonner  suggested  use  of  'plutonium/  " 

Nature,  160,  164  (1947). 

(71)  CUNNINGHAM,  B.  B.  and  L.  B.  WERNER,  "The  first  isolation  of  plutonium," 

/.  Am.  Chem.  Soc.,  71,  1521-8  (1949). 

(72)  SEABORG,  G.  T.,  "The  transuranium  elements,"  Science,  104,  379-86  (1946). 

(73)  HARVEY,  B.  G.,  H.  G.  HEAL,  A.  C.  MADDOCK,  and  E.  L.  ROWLEY,  "The  chem- 

istry of  plutonium,"  /.  Chem.  Soc.,  1947,  1010-21. 

( 74 )  SMITH,  C.  S .,  "Properties  of  plutonium  metal,"  Phys.  Rev.,  94,  1068-9  ( 1954 ) . 

(75)  SEABORG,  G.  T.  and  M.  L.  PERLMAN,  "Search  for  elements  94  and  93  in 

nature.  Presence  of  94s39  in  pitchblende,"  /.  Am.  Chem.  Soc.,  70,  1571-3 
(1948). 

(76)  GARNER,  C.  S.,  N.  A.  BONNER,  and  G.  T.  SEABORG,  "Search  for  elements  94 

and  93  in  nature.  Presence  of  94s39  in  carnotite,"  /.  Am.  Chem.  Soc.,  70, 
3453-4  (1948). 

(77)  PEPPARD,  D.  F.,  M.  H.  STUDIER,  M.  W.  GERGEL,  G.  W.  MASON,  J.  C.  SUL- 

LIVAN, and  J.  F.  MECH,  "Isolation  of  microgram  quantities  of  naturally 
occurring  plutonium  and  examination  of  its  isotopic  composition,"  ].  Am. 
Chem.  Soc.,  73,  2529-31  (1951). 

(78)  CORVALEN,  M.  I.,  "Concentration  of  plutonium  in  pitchblende,"  Phys.  Rev., 

71,  132  (1947). 

(79)  KATZ,  J.,  H.  A.  KORNBERG,  and  H.  M.  PARKER,  "Absorption  of  plutonium  fed 

chronically  to  rats,"  Am.  J.  Roentgenol.,  Radium  Therapy,  Nuclear  Med., 
73,  303-8  (1955). 

(80)  STREET,  K.,  JR.  and  G.  T.  SEABORG,  "The  separation  of  americium  and  curium 

from  the  rare  earth  elements,"  J.  Am.  Chem.  Soc.,  72,  2790-2  (1950). 

(81)  SEABORG,  G.  T.,  "Plutonium  and  other  transuranium  elements,"  Chem.  Eng. 

News,  24,  3160-1  (1946). 

(82)  WESTRXJM,  C.  F.,  JR,  and  L.  EYRING,  "The  preparation  and  some  properties 

of  americium  metal,"  /.  Am.  Chem.  Soc.,  73,  3396-8  (1951). 

(83)  WALLMANN,  J.  C.,  W.  W.  T.  CRANE,  and  B.  B.  CUNNINGHAM,  "The  prepara- 

tion and  some  properties  of  curium  metal,"  /.  Am.  Chem.  Soc.  73,  493-4 
(1951). 

(84)  PEPPARD,  D.  F.,  P.  R.  GRAY,  and  M.  M.  MARKUS,  "The  actinide-lanthanide 

analogy  as  exemplified  by  solvent  extraction,"  J.  Am.  Chem.  Soc.,  75, 
6063-4  (1953). 

(85)  EMELIUS,  H.  J.,  "Transuranium  and  other  newly  discovered  elements,"  Sci- 

ence Progr.,  38,  609-21  (1950). 

(86)  PANETH,  F.  A.,  "The  making  of  the  elements  97  and  98,"  Nature,  165,  748-9 

(1950). 

(87)  HAISSINSKY,  M.,  "The  position  of  the  cis-  and  trans-uranic  elements  in  the 

periodic  system:    uranides  or  actinides?"  J.  Chem.  Soc.,  1949,  S  241-3. 

(88)  HAISSINSKY,    M.,    "La   place   des   elements    transuraniens    dans    le    systeme 

p<§riodique,"  Experientia,  9,  117-20  (1953). 

(89)  THOMPSON,  S.  G.,  A.  GHIORSO,  and  G.  T.  SEABORG,  "Element  97,"  Phys.  Rev 

77,  838-9  (1950). 

(90)  THOMPSON,  S.   G.,   A.  GHIORSO,  and   G.  T.   SEABORG,   "The  new   element 

berkelium  (atomic  number  97),"  ibid.,  80,  781-9  (1950). 


ELEMENTS    DISCOVERED    BY    ATOMIC    BOMBARDMENT  883 

(91 )  THOMPSON,  S.  G.,  K.  STREET,  JR.,  A.  GHIORSO,  and  G.  T.  SEABORG,  "Element 

98,"  Phys.  Rev.,  78,  298-9  (1950). 

(92)  THOMPSON,  S.  G.,  K.  STREET,  JR.,  A.  GHIORSO,  and  G.  T.  SEABORG,  "The  new 

element  californium  (atomic  number  98),"  ibid.,  80,  790-6  (1950). 

(93)  THOMPSON,  S.  G.,  B.  B.  CUNNINGHAM,  and  G.  T.  SEABORG,  "Chemical  prop- 

erties of  berkelium,"  /.  Am.  Chem.  Soc.,  72,  2798-801  (1950). 
(94}     STREET,  K.,  JR.,  S.  G.  THOMPSON,  and  G.  T.  SEABORG,  "Chemical  properties 
of  californium/'  /.  Am.  Chem.  Soc.,  72,  4832-5  (1950). 

( 95 )  ZNOIKO,  A.  P.  and  V.  I.  SEMISHIM,  "The  problem  of  elements  numbered  97 

and  98"  (in  Russian),  Doklady  Akad.  Nauk  S.S.S.R.,  74,  917-19  (1950). 

(96)  THOMPSON,  S.  G.,  A,  GHIORSO,  B.  G.  HARVEY,  and  G.  R.  CHOPPIN,  "Trans- 

curium  isotopes  produced  in  the  neutron  irradiation  of  plutonium,"  Phys. 
Rev.,  93,  908  (1954). 

(97)  HARVEY,  B.  G.,  S.  G.  THOMPSON,  A.  GHIORSO,  and  G.  R.  CHOPPIN,  "Further 

production  of  transcurium  nu elides  by  neutron  irradiation/'  Phys.  Rev., 
93,  1129  (1954). 

(98)  CHOPPIN,  G.  R.,  S.  G.  THOMPSON,  A.  GHIORSO,  and  B.  G.  HARVEY,  "Nuclear 

properties  of  some  isotopes  of  californium,  elements  99  and  100,"  Phys. 
Rev.,  94,  1080-1  (1954). 

(99)  STUDIER,  M.  H.?  P.  R.  FIELDS,  H.  DIAMOND,  J.  F.  MECH,  A.  M.  FRIEDMAN, 

P.  A.  SELLERS,  G.  PILE,  C.  M.  STEVENS,  L.  B.  MAGNUSSON,  and  J.  R. 
HUIZENGA,  "Elements  99  and  100  from  pile-irradiated  plutonium/'  Phys. 
Rev.,  93,  1428  (1954). 

(100)  "99,  100,  and  now  17  atoms  of  101,"  Chem.  Eng.  News,  33,  1956-7  (1955). 

(101)  GHIORSO,  A.,  B.  G.  HARVEY,  G.  R.  CHOPPIN,  S.  G.  THOMPSON,  and  G.  T. 

SEABORG,  "New  element  mendelevium,  atomic  number  101,"  Phys.  Rev., 
98,  1518-19  (1955). 

(102)  GHIORSO,  A.,  S.  G.  THOMPSON,  G.  H.  HIGGINS,  G.  T.  SEABORG,  M.  H.  STUDIER, 

P.  R.  FIELDS,  S.  M.  FRIED,  H.  DIAMOND,  J.  F.  MECH,  G.  L.  PYLE,  J.  R. 
HUIZENGA,  A.  HIRSCH,  W.  M.  MANNING,  C.  I.  BROWNE,  H.  L.  SMITH,  and 
R.  W.  SPENCE,  "New  elements  einsteinium  and  fermium,  atomic  numbers 
99  and  100,"  Phys.  Rev.,  99,  1048-9  (1955). 

(103)  FIELDS,  P.  R.,  A.  M.  FRIEDMAN,  J.  MILSTED,  H.  ATTERLING,  W.  FORSLING, 

L.  W.  HELM,  and  B.  ASTROM,  "Production  of  the  New  Element  102/' 
Phys.  Rev.,  107,  1460-2  (1957). 

(104)  GHIORSO,  A.,  T.  SIKKELAND,  J,  R.  WALTON,  and  G.  T.  SEABORG,  "Attempts  to 

Confirm  the  Existence  of  the  10-Minute  Isotope  of  102,"  Phys.  Rev.  Letters, 
1,  17-18  (1958). 

(105)  GHIORSO,  A.,  T.  SIKKELAND,  J.  R.  WALTON,  and  G.  T.  SEABORG,  "Element  No. 

102,"  Phys.  Rev.  Letters,  1,  1&-21  (1958). 

(106)  "The  New  Elements,  A  Symposium,"  Reprint  of  /.  Chem.  Educ.,  36,  2-44 

(1959).    Chemical  Education  Publishing  Co.,  Easton,  Pa. 


A  list  of  the  chemical  elements 


Atomic  No. 

0 

1 

2 

3 

4 

5 

6 

7 

8 

9 
10 
11 
12 
13 
14 
15 
16 
17 
18 
19 
20 
21 
22 
23 
24 
25 
26 
27 
28 
29 
30 
31 
32 
33 
34 
35 
36 
37 
38 
39 
40 
41 

42 
43 
44 
45 


Name 
neutron 
hydrogen 
helium 
lithium 
beryllium 
boron 
carbon 
nitrogen 
oxygen 
fluorine 
neon 
sodium 
magnesium 
aluminum 
silicon 
phosphorus 
sulfur 
chlorine 
argon 
potassium 
calcium 
scandium 
titanium 
vanadium 
chromium 
manganese 
iron 
cobalt 
nickel 
copper 
zinc 
gallium 
germanium 
arsenic 
selenium 
bromine 
krypton 
rubidium 
strontium 
yttrium 
zirconium 
niobium 

( columbium ) 
molybdenum 
technetium 
ruthenium 
rhodium 


Symbol 

n 

H 

He 

Li 

Be 

B 

C 

N 

O 

F 

Ne 

Na 

Mg 

Al 

Si 

P 

S 

€1 

Ar 

K 

Ca 

Sc 

Ti 

V 

Cr 

Mn 

Fe 

Co 

Ni 

Cu 

Zn 

Ga 

Ge 

As 

Se 

Br 

Kr 

Rb 

Sr 

Y 

Zr 

Nb 


Mo 
Tc 
Ru 
Rh 


(Cb) 


1955 
Atomic  Wt. 

1.0080 

4.003 

6.940 

9.013 
10.82 
12.011 
14.008 
16.0000 
19.00 
20.183 
22.991 
24.32 
26.98 
28.09 
30.975 

32.066±0.003 
35.457 
39.944 
39.100 
40.08 
44.96 
47.90 
50.95 
52.01 
54.94 
55.85 
58.94 
58.71 
63.54 
65.38 
69.72 
72.60 
74.91 
78.96 
79.916 
83.80 
85.48 
87.63 
88.92 
91.22 
92.91 

95.95 

99* 
101.1 
102.91 


Mass  number  of  the  isotope  of  longest  known  half-life 

884 


A  LIST  OF  THE  CHEMICAL  ELEMENTS 


885 


Atomic  No. 

46 

47 

48 

49 

50 

51 

52 

53 

54 

55 

56 

57 

58 

59 

60 

61 

62 

63 

64 

65 

66 

67 

68 

69 

70 

71 

72 
73 
74 
75 
76 
77 
78 
79 
80 
>81 
82 
83 
84 
85 
86 
87 
88 
89 
90 
91 
92 
93 
94 
95 
96 
97 
98 
99 
100 
101 
102 


Name 

palladium 

silver 

cadmium 

indium 

tin 

antimony 

tellurium 

iodine 

xenon 

cesium 

barium 

lanthanum 

cerium 

praseodymium 

neodymium 

promethium 

samarium 

europium 

gadolinium 

terbium 

dysprosium 

holmium 

erbium 

thulium 

ytterbium 

lutetium 

hafnium 

tantalum 

tungsten 

rhenium 

osmium 

iridium 

platinum 

gold 

mercury 

thallium 

lead 

bismuth 

polonium 

astatine 

radon 

francium 

radium 

actinium 

thorium 

protactinium 

uranium 

neptunium 

plutonium 

americium 

curium 

berkelium 

californium 

einsteinium 

fermium 

mendelevium 

nobelium 


Symbol 

Pd 

Ag 

Cd 

In 

Sn 

Sb 

Te 

I 

Xe 

Cs 

Ba 

La 

Ce 

Pr 

Nd 

Pm 

Sm 

Eu 

Gd 

Tb 

Dy 

Ho 

Er 

Tm 

Yb 

Lu 

Hf 

Ta 

W 

Re 

Os 

Ir 

Pt 

Au 

Hg 

Tl 

Pb 

Bi 

Po 

At 

Rn 

Fr 

Ra 

Ac 

Th 

Pa 

U 

Np 

Pu 

Am 

Cm 

Bk 

Cf 

Es 

Fm 

Md 

No 


1955 
Atomic  Wt. 

106.4 

107.880 

112.41 

114.82 

118.70 

121.76 

127.61 

126.91 

131.30 

132.91 

137.36 

138.92 

140.13 

140.92 

144.27 

145* 

150.35 

152.0 

157.26 

158.93 

162.51 

164.94 

167.27 

168.94 

173.04 

174.99 

178.50 

180.95 

183.86 

186.22 

190.2 

192.2 
195.09 

197.0 

200.61 

204.39 

207.21 

209.00 

210 

210* 

222 

223* 

226.05 

227 

232.05 

231 

238.07 

237* 

242* 

243* 

245* 

249* 

249* 


256* 


Chronology  of  element  discovery 


Sixteenth  Century 

1524  Hernando  Cortes  mentions  coins  made  of  tin  from  Taxco  that 

were  in  use  in  Mexico. 
1541  Francisco  Vazquez  de  Coronado  observes  a  copper  ornament 

worn  by  an  Indian  chief,  in  what  is  now  the  southwestern 

part  of  the  United  States. 

1570  Pedro  Fernandes  de  Velasco  demonstrates  his  cold  amalgama- 

tion process  for  the  recovery  of  silver  from  the  ores  of 

Mount  Potosi  (Bolivia). 
1590  The  Chinese  encyclopedia  of  materia  medica,  the  Pen  Ts'ao 

Kan-Mu,  describes  the  uses  of  arsenic. 
1590  Father  Jose  de  Acosta  describes  the  metallurgy  of  silver  and 

mercury  in  the  New  World. 


Seventeenth  Century 

1602  John  Brereton  describes  the  copper  artifacts  of  the  Indians  of 

Virginia. 
1604  The  "Triumphal  Chariot  of  Antimony"  by  Pseudo-Basilius 

Valentinus  is  published. 
1604  Birth  of  J.  R.  Glauber. 

Jan.  25,  1627        Birth  of  Robert  Boyle  in  Ireland.     Independent  discoverer  of 

phosphorus. 

1630  Birth  of  Johann  Kunckel,  early  writer  on  phosphorus. 

1637  A  Chinese  book  entitled  "Tien  kong  kai  ou"  describes  the 

metallurgy  and  uses  of  zinc. 

1640  Father  A.  A.  Barba  of  Potosi  publishes  the  first  treatise  on 

American  metallurgy. 

1641  Birth  of  Dr.  John  Mayow  in  London.     Author  of  an  early 

theory  of  combustion. 

Nov.  17,  1645      Birth  of  Nicolas  Lemery  at  Rouen, 
1649  Johann  Schroeder  describes  two  methods  of  preparing  metallic 

arsenic. 

1652  Birth  of  Willem  Homberg. 

1660  Birth  of  G.  E,  StahL 

1665  Robert  Hooke  gives  a  theory  of  combustion  in  his  book 

"Micro  graphia." 

1668  Birth  of  Herman  Boerhaave. 

1669  The  alchemist  Brand  of  Hamburg  discovers  phosphorus;  but 

see  footnote  on  p.  110. 


CHRONOLOGY  OF  ELEMENT  DISCOVERY 


887 


1670  Heinrich  Sehwanhard  etches  glass  with  a  mixture  of  fluorspar 

and  a  concentrated  acid. 

1670  Death  of  J.  R.  Glauber. 

1671  Robert  Boyle  prepares  hydrogen    ("inflammable  solution  of 

Mars")  by  dissolving  iron  in  dilute  hydrochloric  or  sulfuric 
acid. 

1672  Birth  of  E.-F.  Geoffrey. 

1674  Dr.  John  Mayow  recognizes  that  the  air  has  two  constituents. 

1677  Birth  of  Louis  Lemery 

1679  Death  of  Dr.  Mayow. 

1683  Johann  Bohn  distinguishes  between  "cubic  saltpeter"  (sodium 

nitrate)  and  ordinary  "prismatic  saltpeter." 

1683  Birth  of  Caspar  Neumann. 

1688  Bernard  S.  Albinus  (Weiss)  mentions  the  presence  of  phos- 

phorus in  the  ash  of  mustard  and  cress. 

1691  Death  of  Robert  Boyle. 

June  26,  or  July  Birth  of  Georg  Brandt,  the  discoverer  of  cobalt,  at  Riddar- 
21,  1694  hytta,  Vestmanland,  Sweden. 

1695  Nehemiah  Grew  publishes  a  dissertation  on  Epsom  salt. 

1700  Nicolas  Lemery  describes  hydrogen. 

1700  Birth  of  H.-L.  du  Hamel  du  Monceau. 


Eighteenth  Century 

1701  A  posthumous  edition  of  Turquet  de  Mayerne  mentions  the 

flammability  of  hydrogen. 

1702  Death  of  Kunckel. 

1702  Willem  Homberg  prepares  "sedative  salt"  (boric  acid) . 

1702  G.  E.  Stahl  distinguishes  between  the  natural  and  the  artificial 

alkali  (soda  and  potash). 
1705  Birth  of  Vincenzo   Menghini,   the  first   to   demonstrate   the 

presence  of  iron  in  red  blood  corpuscles. 

1707  Nicolas  Lemery  publishes  his  "Treatise  on  Antimony." 

Mar.  3,  1709         Birth  of  Andreas  Sigismund  Marggraf  at  Berlin. 
June  19,  1715       Death  of  Nicolas  Lemery. 

1715  Death  of  Willem  Homberg. 

1716  Birth  of  Don  Antonio  de  Ulloa. 
1718  Birth  of  P.-J.  Macquer. 

Dec.  23,  1722  Birth  of  Axel  Fredrik  Cronstedt,  the  discoverer  of  nickel,  in 

Sodermanland,  Sweden. 

1731  Death  of  E.-F.  Geoffrey. 

Oct.  10,  1731  Birth  of  Henry  Cavendish  at  Nice. 

(old  style)  Birth  of  Joseph  Priestley  at  Fieldhead,  Yorkshire,  near  Leeds. 
Mar.  13,  1733 

1734  Death  of  G.  E.  Stahl. 


888 


DISCOVERY  OF  THE  ELEMENTS 


1735 

1736 


1737 
1737 

1737-38 

1738 
1740 

July  1,  1740 
1740-41 

1742 
1742 
Dec.  9  (or  19), 

1742 
1743 

Aug.  26, 1743 
Dec.  1,  1743 

1745 

Aug.  19,  1745 

1746 

Oct.  2,  1746 

1748 

Nov.  3,  1749 

1750 
1751 
1752 
1753 

1754 

June  15,  1754 

Oct.  11,  1755 

1755 


Birth  of  Torbern  Bergman. 

H  -L   du  Hamel  du  Monceau  demonstrates  that  the  mineral 

alkali  (soda)  is  a  constituent  of  common  salt,  ot  Glaubers 

salt,  and  of  borax,  and  prepares  sodium  carbonate  from  salt. 
Death  of  Caspar  Neumann. 
Jean  Hellot  prepares  a  button  of  metallic  bismuth  and  makes 

public  the  secret  process  for  preparing  phosphorus. 
Georg  Brandt  isolates  cobalt. 
Death  of  Herman  Boerhaave. 
J.  H.  Pott  states  that  pyrolusite  contains  the  calx  of  a  new 

metal. 
Birth  of  Midler  von  Reichenstein,  the  discoverer  of  tellurium, 

at  Nagyszeben,  Transylvania  (Sibiu,  Ardeal) . 
Charles  Wood  finds  in  Jamaica  some  platinum  which  has  come 

from  Cartagena,  New  Spain. 
Anton  von  Svab  distills  zinc  from  calamine. 
Birth  of  Baron  Ignaz  Edler  von  Born. 
Birth  of  Carl  Wilhelm  Scheele  at  Stralsund,  Swedish  Pome- 

rania. 

Death  of  Louis  Lemery. 
Birth  of  Lavoisier  in  Paris. 
Birth  of  Martin  Heinrich  Klaproth  at  Wernigerode  in  the 

Harz,     One  of  the  first  to  investigate  uranium,  titanium, 

and  cerium. 

V.  Menghini  detects  iron  in  red  blood  corpuscles. 
Birth  of  Johan  Gottlieb  Garni,  the  discoverer  of  manganese, 

at  Xoxna,  South  Helsingland,  Sweden. 
Marggraf  prepares  metallic  zinc  by  reduction  of  calamine. 
Birth  of  Peter  Jacob  Hjelm,  the  discoverer  of  molybdenum, 

at  Sunnerbo  Harad,  Sweden. 
Don  Antonio  de  Ulloa  describes  platinum. 
Birth  of  Daniel  Rutherford,  the  discoverer  of  nitrogen,  at 

Edinburgh. 

Dr.  William  Brownrigg  describes  platinum. 
Cronstedt  isolates  nickel. 

H.  T.  Scheffer  fuses  platinum  with  the  aid  of  arsenic. 
Claude-Frangois  Geoffrey's  research  on  "The  Chemical  Analy- 
sis of  Bismuth"  is  published. 
Marggraf  prepares  and  characterizes  alumina. 
Birth  of  Juan  Jose  de  Elhuyar. 
Birth  of  Don  Fausto  de  Elhuyar  at  Logrono,  Spain.    With  his 

brother,  Don  Juan  Jose  he  isolated  tungsten  (wolfram) , 
Dr.  Joseph  Black  of  Edinburgh  recognizes  magnesia  alba  to 

be  distinct  from  lime. 


CHRONOLOGY  OF  ELEMENT  DISCOVERY 


889 


1758-59  Marggraf  independently  recognizes  the  distinction  between 

magnesia  and  lime,  and  uses  flame  tests  to  distinguish  be- 
tween the  nitrates  of  sodium  and  potassium. 

June  5,  1760  Birth  of  Johan  Gadolin,  the  discoverer  of  yttria,  at  Abo, 
Finland. 

Nov.  30,  1761  Birth  of  Smithson  Tennant,  the  discoverer  of  osmium  and 
iridium,  at  Wensleydale,  Yorkshire. 

Dec.  25,  1761  Birth  of  the  Reverend  William  Gregor,  the  discoverer  of 
titanium,  in  Trewarthenick,  Cornwall. 

May  16,  1763  Birth  of  N.-L.  Vauquelin,  the  discoverer  of  chromium  and 
beryllium,  at  St.  Andre  des  Berteaux. 

Nov.  10,  1764  Birth  of  A.  M.  del  Rio,  discoverer  of  vanadium  (erythronium) , 
in  Madrid. 

Jan.  2,  1765  Birth  of  Charles  Hatchett,  the  discoverer  of  columbium  (nio- 
bium), in  London. 

Aug.  19, 1765       Death  of  Cronstedt  in  Saters  parish,  near  Stockholm. 

Aug.  6,  1766  Birth  of  Dr.  William  Hyde  Wollaston,  the  discoverer  of 
palladium  and  rhodium,  at  East  Dereham,  Norfolkshare. 

Dec.,  1766  Birth  of  Wilhelm  Hisinger,  the  discoverer  of  the  earth  ceria. 

Berzelius,  Hisinger,  and  Klaproth  all  investigated  this  earth, 
the  latter  independently. 

Jan.  16,  1767  Birth  of  Anders  Gustaf  Ekeberg,  the  discoverer  of  tantalum, 
at  Stockholm. 

Apr.  29,  1768       Death  of  Georg  Brandt  at  Stockholm. 

1769  Scheele  and  Gahn  isolate  phosphorus  from  bones. 

1770  P.  S.  Pallas  describes  the  "red  lead  of  Siberia"  (crocoite),  in 

which  Vauquelin  later  discovered  chromium. '  This  mineral 
had  been  analyzed  four  years  earlier  by  J.  G.  Lehmann. 

1771  Scheele  describes  hydrofluoric  acid. 

1772  Daniel  Rutherford  discovers  nitrogen.      (Scheele,  Priestley, 

and  Cavendish  discover  it  independently  at  about  the 
same  time. ) 

1772-82  Baron  Carl  von  Sickingen  devises  a  process  for  making  plat- 

inum malleable. 

1774  Birth  of  J.-F.  Coindet. 

Apr.,  1774  Pierre  Bayen  prepares  oxygen  by  heating  mercuric  oxide. 

1774  Scheele  publishes  his  famous  treatise  "Concerning  Manganese 

and  its  Properties,"  which  led  to  the  discovery  of  three 
elements:  manganese,  barium,  and  chlorine. 

Aug.  1,  1774  Priestley  prepares  oxygen.  (Scheele  prepared  it  before  this, 
but  his  results  were  not  published  until  1777.) 

1774  Gahn  isolates  manganese. 

1775  Johan  Arvidsson  Afzelius  publishes  his  doctor's  dissertation 

defending  Bergman's  belief  in  the  elementary  nature  of 
nickel.      (He  sometimes  signed  his  name  Johan  Afzelius 
-  ~  Arvidsson.) 


890  DISCOVERY  OF  THE  ELEMENTS 

Aug.  2,  1776         Birth  of  Friedrich  Stromeyer,  the  discoverer  of  cadmium,  at 

Gottingen. 
Feb.  8,  1777         Birth  of  Bernard  Courtois,  the  discoverer  of  iodine,  at  Dijon. 

1777  Lavoisier  overthrows  the  phlogiston  theory  and  demonstrates 

the  true  nature  of  combustion. 
May  4,  1777         Birth  of  Louis-Jacques  Thenard. 
Aug.  14,  1777       Birth  of  Hans  Christian  Oersted. 

1778  Scheele   distinguishes  between   graphite   and  the   ore   then 

known  as  "molybdenum." 

Dec.  6,  1778  Birth  of  Gay-Lussac  at  Saint-Leonard. 

Dec.  17,  1778  Birth  of  Sir  Humphry  Davy  at  Penzance,  Cornwall. 

1779  Scheele  distinguishes  between  lime  and  baryta. 
Aug.  20,  1779  Birth  of  Berzelius  at  Vaversunda,  Sweden. 

1780  Birth  of  }.  W.  Dobereiner,  the  discoverer  of  the  "triads." 

1781  Scheele  discovers  tungstic  acid. 
1781  Hjelm  isolates  molybdenum. 
Aug.  7,  1782  Death  of  Marggraf. 

1783  Discovery  of  tellurium  by  Miiller  von  Reichenstein. 

1783  Discovery  of  tungsten  by  the  de  Elhuyar  brothers. 

1783  P.-F.    Chabaneau   patents    a   process   for   making   platinum 

malleable. 

1784  Death  of  Torbern  Bergman. 

1784  Death  of  P.-J.  Macquer. 

1785  R.  E.  Raspe  shows  that  tungsten  hardens  steel. 
May  21,  1786      Death  of  Scheele. 

June  2,  1787  Birth  of  Nils  Gabriel  Sefstrom,  the  rediscoverer  of  vanadium, 
in  Ilsbo  Socken,  Sweden.  Although  vanadium  is  now 
known  to  be  identical  with  del  Rio's  "erythronium,"  the 
latter  chemist  did  not  distinguish  clearly  between  chromium 
and  the  new  element. 

1789  Klaproth  observes  uranium  in  pitchblende,  but  does  not  isolate 

it.    In  the  same  year  he  discovers  the  earth  zirconia. 

1790  Hjelm  publishes  his  first  paper  on  molybdenum.     He  had 

isolated  it  as  early  as  1781. 

1790  Adair  Crawford  recognizes  strontia  as  a  new  earth. 

1791  The  Rev.  William  Gregor  discovers  the  oxide  of  a  new  metal, 

titanium. 

1791  Death  of  Baron  von  Born. 

Jan.  12,  1792       Birth  of  Johan  August  Arfwedson,  the  discoverer  of  lithium, 

at  Skagerholms-Bruk,  Skaraborgs  Lan. 
May  8,  1794          Death  of  Lavoisier  on  the  guillotine. 
1794  Gadolin  discovers  the  earth  yttria. 

May  29,  1794  Birth  of  A.-A.-B.  Bussy  at  Marseilles.  He  obtained  mag- 
nesium in  coherent  form. 


CHRONOLOGY  OF  ELEMENT  DISCOVERY  891 

1795  Klaproth  rediscovers  titanium,  but  does  not  succeed  in  isolat- 

ing it. 

1795  Death  of  Don  Antonio  de  Ulloa. 

Jan.  23,  1796  Birth  of  Karl  Karlovich  Klaus,  the  discoverer  of  ruthenium, 
at  Dorpat,  Estonia. 

1796  Smithson  Tennant  proves  that  the  diamond  consists  solely  of 

carbon. 

Sept.  10,  1797  Birth  of  Carl  Gustav  Mosander,  the  discoverer  of  lanthanum 
and  didymium,  at  Kalmar,  Sweden. 

1797-98  Vauquelin  recognizes  beryllium  (glucinum)  and  isolates 

chromium.  Beryllium  was  first  isolated  in  1828  by 
Wohler. 

Jan.  25,  1798  Klaproth  brings  Miiller  von  Reichenstein's  discovery  of  tellu- 
rium to  the  attention  of  German  chemists. 

Feb.  19,  1799  Birth  of  Ferdinand  Reich,  the  discoverer  of  indium,  at  Bern- 
burg. 

July  31,  1800        Birth  of  Friedrich  Wohler  at  Eschersheim,  Germany. 

1800  J.  B.  de  Andrada  describes  petalite  and  spodumene,  minerals 

in  which  J.  A.  Arfwedson  afterward  discovered  lithium. 

Nineteenth  Century 

1801  Robert  Hare  fuses  platinum.    Two  years  later  he  volatilizes  it. 
1801                       Del  Rio  recognizes  the  presence  of  a  new  metal  "eiythronium" 

(vanadium)  in  a  lead  ore  from  Zimapan,  Mexico.  He  after- 
ward confuses  it  with  chromium. 

1801  Hatchett  observes  columbium  (niobium)  in  an  ore  from  New 

England. 

1802  Ekeberg  discovers  the  earth  tantala. 

Sept.  30,  1802      Birth  of  A.-J.  Balard,  the  discoverer  of  bromine,  at  Mont- 

pellier. 
Mar.  17,  1803      Birth  of  Carl  Lowig,  independent  discoverer  of  bromine. 

1803  Klaproth,  Berzelius,  and  Hisinger  analyze  cerite  and  discover 

the  earth  ceria. 

1803  Wollaston  discovers  palladium  and  rhodium. 
Feb.  6,  1804         Death  of  Priestley  at  Northumberland,  Pa. 

1804  Smithson  Tennant  discovers  osmium  and  iridium. 

Oct.  6,  1807          Davy   isolates    potassium.      A    few    days    later   he    isolates 

sodium. 
1808  Davy  isolates  barium,  strontium,  calcium,  and  magnesium. 

1808  Gay-Lussac  and  Thenard  isolate  boron.     Davy  isolates  it  in- 

dependently. 

1809  Gay-Lussac  and  Thenard  prove  that  sulfur  is  an  element. 
1809  Dr.  Wollaston  makes  the  erroneous  conclusion  that  tantalum 

and  columbium  are  identical. 
Feb.  24,  1810      Death  of  Cavendish. 


892  DISCOVERY  OF  THE  ELEMENTS 

Nov.  15,  1810      Davy  announces  his  proof  of  the  elementary  nature  of  chlorine 

to  the  Royal  Society. 
1811  Bernard  Courtois  discovers  iodine. 

Mar.   24    (or  . 

Feb.  24) ,          Birth  of  Eugene-Melchior  Peligot,  the  first  to  isolate  uranium. 

1811 

Mar.  31,  1811  Birth  of  Robert  Bunsen  at  Gottingen. 

Feb.  11,  1813  Death  of  Ekeberg  at  Upsala. 

Oct.  7,  1813  Death  of  Hjelm  at  Stockholm. 

1813  Clement  confirms  the  discovery  of  iodine  by  Courtois. 

1814  Fraunhofer  discovers  the  dark  lines  in  the  sun's  spectrum. 
1814  Gay-Lussac  publishes  his  classical  research  on  iodine. 
Feb.  22,  1815  Death  of  Tennant  at  Boulogne-sur-Mer. 

Jan.  1,  1817          Death  of  Klaproth  at  Berlin. 

Apr.  24,  1817       Birth  of  Jean  Galissard  de  Marignac,  the  discoverer  of  ytterbia 
and  gadolinia,  at  Geneva,  Switzerland. 

June  11   (or  July 

11),  1817         Death  of  William  Gregor. 
1817  Arfwedson  discovers  lithium. 

1817  Stromeyer  discovers  cadmium 

1818  Berzelius  discovers  selenium. 

Mar.  11,  1818      Birth  of  Henri   Sainte-Claire  Deville   on  the  island  of   St. 

Thomas  in  the  Antilles. 

Dec.  8,  1818        Death  of  Gahn  at  Stockholm. 
Dec.  15,  1819      Death  of  Daniel  Rutherford. 

1820  J.-F.  Coindet  prescribes  iodine  in  goiter  therapy. 

1820  Birth   of  Beguyer   de  Chancourtois,   the   discoverer   of   the 

"telluric  screw." 
July  15,  1820       Birth  of  Claude-August  Lamy  at  Nery,  France.    He  prepared 

thallium  in  the  metallic  state. 

1822  Discovery  of  platinum  in  the  Urals. 

1823  William  Prout  detects  free  hydrochloric  acid  in  the  stomach. 

1824  Berzelius  isolates  amorphous  silicon. 
Mar.  12,  1824      Birth  of  Gustav  Kirchhoff  at  Konigsberg. 

Nov.  21,  1824      Birth  of  Hieronymus  Theodor  Richter,  the  first  to  observe  the 
indigo  line  of  indium. 

1824  Berzelius  isolates  impure  zirconium. 

1825  Oersted  isolates  impure  aluminum. 

Oct.  12,  1825  Death  of  M  filler  von  Reichenstein  at  Vienna. 

(1826?) 

1825  Berzelius  prepares  impure  amorphous  titanium. 

1825  Carl  Lowig  isolates  bromine. 

1826  P.  G.   Sobolevsku  and  V.  V.   Liubarskii  prepare  malleable 

platinum. 


CHRONOLOGY  OF  ELEMENT  DISCOVERY  893 

1826  Balard  isolates  bromine.     His  results  were  published  before 

those  of  Lowig. 

1827  Wohler  isolates  aluminum. 

1828  Wohler  isolates  beryllium.    Bussy  isolates  it  independently. 
Dec.  22,  1828      Death  of  Dr.  Wollaston  in  London.     His  specifications  for 

making  platinum  malleable  were  circulated  at  the  same 
time  as  the  news  of  his  death. 

1829  Berzelius  separates  the  earth  thoria  from  thorite. 

1829  Dobereiner  observes  the  triads. 

May  29,  1829      Death  of  Davy  at  Geneva,  Switzerland. 

Nov.  14,  1829      Death  of  Vauquelin  at  the  Chateau  des  Berteaux. 

1830  Sef strom  rediscovers  vanadium. 

Aug.  19,  1830       Birth  of  Lothar  Meyer  at  Varel  on  the  Jade. 

1831  Bussy  obtains  magnesium  in  compact  form.     (Davy  had  iso- 

lated it  in  1808.) 

June  17,  1832      Birth  of  Sir  William  Crookes. 
Jan.  6,  1833          Death  of  Don  Fausto  de  Elhuyar  at  Madrid. 
Jan.  7,  1833          Birth  of  Sir  Henry  E.  Roscoe,  the  first  to  liberate  metallic 

vanadium. 

1834  Death  of  J.-F.  Coindet. 

Feb.  8  (Jan.          Birth  of  Mendeleev  at  Tobolsk,  Siberia, 

27),  1834 

Aug.   18,   1835     Death  of  Stromeyer  at  Gottingen. 
1837  Birth  of  J.  A.  R.  Newlands,  the  discoverer  of  the  law  of 

octaves. 

Apr.  18,  1838      Birth  of  Lecoq  de  Boisbaudran  at  Cognac. 
Sept.  27,  1838     Death  of  Bernard  Courtois  in  Paris. 
Dec.  26,  1838      Birth  of  Clemens  Winkler,  the  discoverer  of  germanium,  at 

Freiberg. 

1839  Mosander  discovers  lanthana. 

Feb.  10,  1840       Birth   of  Per  Teodor   Cleve,   the   discoverer   of  thulium,   at 

Stockholm. 
May  27,  1840       Birth  of  Lars  Fredrik  Nilson,  the  discoverer  of  scandium,  in 

Ostergotland,  Sweden. 
1841  Peligot  isolates  uranium. 

1841  Mosander  discovers  didymia. 

Oct.  28,  1841       Death  of  J.  A.  Arfwedson  at  his  Hedenso  estate. 
Nov.  12,  1842      Birth  of  John  William   Strutt,   Lord   Rayleigh,   at   Terling, 

England. 

1843  Mosander  separates  terbia  and  erbia  from  gadolinite. 

1844  Klaus  discovers  ruthenium. 
Nov.  30,  1845      Death  of  Sefstrom  at  Stockholm. 

1847  E.    Harless    detects    copper   in   the   blood    of   the    octopus 

Eledone. 
Mar.  10,  1847      Death  of  Hatchett  at  Chelsea. 


894 


DISCOVERY  OF  THE  ELEMENTS 


Aug.  7,  1848  Death  of  Berzelius  at  Stockholm. 

Mar.  23,  1849  Death  of  del  Rio  in  Mexico. 

Mar.  24,  1849  Death  of  Dobereiner. 

May  9,   1850  Death  of  Gay-Lussac  in  Paris. 

Mar.  9,  1851  Death  of  Oersted. 

Jan.  1,  1852  Birth  of  E.-A.  DemarQay,  the  discoverer  of  europium. 

June  28,  1852  Death  of  Hisinger. 

Aug.  15,  1852  Death  of  Gadolin. 

Sept.  28,  1852  Birth  of  Henri  Moissan  in  Paris. 

Oct.  2,  1852  Birth  of  Sir  William  Ramsay  at  Glasgow. 

1854  David  Alter  observes  that  each  element  has  a  characteristic 

spectrum. 

1854  Henri  Sainte-Claire  Deville  perfects  an  industrial  process  for 

aluminum  and  prepares  the  first  crystalline  silicon. 

June  21,  1857  Death  of  Thenard. 

Sept.  1,  1858  Birth  of  Carl  Auer,  Baron  von  Welsbach. 

Oct.  15,  1858  Death  of  Mosander. 

May  15,  1859  Birth  of  Pierre  Curie. 

1859  Invention  of  the  spectroscope  by  Kirchhoff  and  Bunsen. 

1859  The  first  petroleum  well  in  the  United  States  is  drilled  at 

Titusville,  Pennsylvania. 

May  10,  1860  Bunsen  and  Kirchhoff  announce  the  discovery  of  cesium. 

Feb.  23,  1861  Bunsen  and  Kirchhoff  announce  the  discovery  of  rubidium. 

Spring,  1861  Crookes  observes  the  green  line  of  thallium. 

Spring,  1862  Lamy  prepares  an  ingot  of  metallic  thallium. 

1862  Beguyer  de  Chancourtois  draws  his  "telluric  screw/' 

1863  Birth  of  P.-L.-T.  Heroult  and  of  Charles  Martin  Hall,  inde- 

pendent discoverers  of  the  electrolytic  process  for  prepar- 
ing metallic  aluminum. 
Summer,  1863      Reich  and  Richter  discover  indium. 

1864  Newlands   and   Lothar    Meyer    independently    arrange    the 

elements  in  series  and  families. 
Mar.  24,  1864      Death  of  Klaus. 

Nov.  7,  1867       Birth  of  Marie  Sklodowska  (Mme.  Curie)  at  Warsaw,  Poland. 
1868  Janssen  and  Lockyer  independently  observe  the  D  line  of 

helium  in  the  sun's  chromosphere. 
July  9,  1868         Birth  of  N.  A.  Langlet. 
June  16,  1869      Roscoe  announces  the  isolation  of  vanadium. 

*869  Lothar  Meyer  and  Mendeleev  independently  discover   the 

periodic  system. 

1870  Birth  of  B.  B.  Boltwood,  the  discoverer  of  ionium. 

Jan.  24,  1872       Birth  of  Morris  William  Travers  at  London. 

April  12,  1872      Birth  of  Georges  Urbain,  the  discoverer  of  lutetium. 


CHRONOLOGY  OF  ELEMENT  DISCOVERY  895 

1873  Dennis  Searle  and  E.  M.  Skillings  discover  the  borax  deposits 

of  California. 

Aug.  27,  1875  Boisbaudran  discovers  gallium,  the  first  element  to  be  dis- 
covered with  the  aid  of  the  spark  spectrum. 

Oct.,  1875  Lewis  Reeve  Gibbes  presents  his  "Synoptical  Table  of  the 

Elements." 

Mar.  30,  1876      Death  of  Balard  at  Paris. 

1878  Marignac  separates  ytterbia  from  erbia. 
Mar.  20,  1878      Death  of  Lamy  at  Paris. 

1879  Boisbaudran  discovers  samaria, 

1879  Nilson  discovers  scandium  (eka-boron). 

1879  Cleve  discovers  holmia  and  thulia.     The  former  had  been 

discovered  independently  by  Soret  in  1878. 

Apr.  27,  1880  Birth  of  Charles  James  near  Northampton,  England. 

Jan.  1,  1881  Death  of  Henri  Sainte-Claire  Deville  at  Boulogne-sur-Seine. 

Feb.  1,  1882  Death  of  Bussy  at  Paris. 

Apr.  27,  1882  Death  of  Ferdinand  Reich. 

Sept.  237  1882  Death  of  Wohler. 

1885  Birth  of  Georg  von  Hevesy  in  Budapest.    Co-discoverer  with 

Dirk  Coster  of  the  element  hafnium. 

June  18,  1885  Auer  von  Welsbach  announces  his  separation  of  didymia  into 
praseodymia  and  neodymia. 

1886  Death  of  Beguyer  de  Chancourtois. 

1886  Boisbaudran  discovers  dysprosia  and  gadolinia,  but  finds  that 

the  latter  is  identical  with  an  oxide  discovered  by  Marignac 

in  1880. 

Feb.  6,  1886        Winkler  discovers  germanium. 
Feb.  23,  1886       Charles  Martin  Hall  produces   electrolytic   aluminum.     Dr. 

Heroult  made  the  same  discovery  independently  at  about 

the  same  time. 

June  26,  1886       Moissan  isolates  fluorine. 
Oct.  17,  1887       Death  of  Kirchhoff. 
Nov.  23,  1887      Birth  of  Moseley  at  Weymouth,  England. 
Apr.  15,  1890       Death  of  Peligot  in  Paris. 
1892  Lord  Rayleigh  finds  that  atmospheric  nitrogen  is  heavier  than 

nitrogen  from  the  decomposition  of  ammonia. 

1894  Ramsay  and  Rayleigh  announce  the  discovery  of  argon 
Apr.  15,  1894      Death  of  Marignac. 

1895  Ramsay  and  Cleve  independently  discover  helium. 
Apr.  11,  1895       Death  of  Lothar  Meyer. 

May  30,  1898  Ramsay  and  Travers  discover  krypton, 

June,  1898  Ramsay  and  Travers  discover  neon.  _ 

July  12,  1898  Ramsay  and  Travers  discover  xenon. 

July,  1898  Mme.  Curie  discovers  polonium. 


896 


DISCOVERY  OF  THE  ELEMENTS 


July  29,  1898  Death  of  J.  A.  R.  Newlands. 

Sept.  25,  1898  Death  of  Hieronymus  Richter. 

Dec.   1898  M.  and  Mme.  Curie  discover  radium. 

1898'  Mme.  Curie  and  G.  C.  Schmidt  independently  discover  the 

radioactivity  of  thorium. 

May  14, 1899  Death  of  Nilson. 

Aug.  16,  1899  Death  of  Bunsen. 

1899  Debierne  discovers  actinium. 

1900  Dorn  discovers  radon  (radium  emanation) . 
1900  Sir  William  Crookes  discovers  uranium  X^ 


Twentieth  Century 

1901  Demargay  discovers  europium. 

1902  Rutherford  and  Soddy  discover  thorium  X. 

1904  B.  B.  Boltwood,  H.  N.  McCoy,  and  J.  W.  Strutt  prove  inde- 

pendently that  radium  is  produced  by  spontaneous  trans- 
mutation of  uranium. 

Oct.  8,  1904          Death  of  Winkler. 

1904  Death  of  Demargay  at  Paris. 

1904-5  Giesel  and  Godlewski  independently  discover  actinium  X. 

1905  L.  B.  Mendel  and  H.  C.  Bradley  discover  zinc  in  the  liver  and 

respiratory  protein  of  the  snail  Sycotypus. 

1905  Hahn  discovers  radiothorium  and  mesothorium  I. 
June  18,  1905       Death  of  Cleve  at  Upsala. 

1906  Hahn  discovers  radioactinium. 

1906  Richard  Willstatter   detects   magnesia   in   the    ash   of   pure 

chlorophyll. 
Apr.  19,  1906       Death  of  Pierre  Curie. 

1907  H.  N.  McCoy  and  W.  H.  Ross  clearly  recognize  the  existence 

of  isotopes,  or  chemically  inseparable  elements. 
1907  Boltwood  discovers  ionium.    This  element  was  independently 

discovered  by  Hahn  and  Marckwald. 
Feb.  2,  1907         Death  of  Mendeleev. 
Feb.  20,  1907       Death  of  Moissan. 
1907  Urbain  discovers  lutetium. 

1907  Von  Bolton  prepares  a  columbium  (niobium)  regulus. 

1909  E.  Weintraub  prepares  pure  fused  boron. 

1910  Mme.  Curie  and  M.  Debierne  isolate  radium  metal. 

1910  M.  A.  Hunter  prepares  titanium  99,9  per  cent  pure. 

1911  Antonoff  discovers  uranium  Y. 
May  28,  1912       Death  of  Boisbaudran. 

1913  Fajans  and  Gohring  discover  uranium  X2  (element  91,  eka- 

tantalum). 


CHRONOLOGY  OF  ELEMENT  DISCOVERY 


897 


Dec.,  1913,  and 

Apr.,  1914 
1914 
1914 

Aug.  10, 1915 
Dec.  18,  1915 
July  23,  1916 
1917 

Apr.  4,  1919 

June  30,  1919 

1921 

Jan.,  1923 

June,  1925 

July  1,  1926 

1927 

1928 

Dec.  10,  1928 

Aug.  4,  1929 

1930 

1932 
1932 


1934 

Jan.  15,  1934 

July  4,  1934 
Sept.,  1934 
March  30,  1936 
Oct.  19,  1937 
Nov.  5,  1938 
1939 


1939 
1939 


1940 


Moseley  publishes  his  papers  on  "The  High  Frequency  Spectra 

of  the  Elements." 

T,  W.  Richards  discovers  a  radioactive  isotope  of  lead. 
Death  of  P.-L.-T.  Heroult  and  C.  M.  Hall. 
Moseley  killed  at  the  Dardanelles. 
Death  of  Sir  Henry  E.  Roscoe. 
Death  of  Ramsay. 
Hahn    and    Meitner    discover    protactinium.       Soddy    and 

Cranston  discover  it  independently. 
Death  of  Sir  William  Crookes. 
Death  of  Lord  Rayleigh. 
Hahn  discovers  uranium  Z. 

Coster  and  Hevesy  discover  hafnium  (element  72) . 
Noddack,  Tacke,  and  Berg  discover  rhenium  (element  75) . 
Death  of  F.  F.  Jewett  in  Honolulu. 
Death  of  Boltwood. 

E.  B.  Hart  et  al.  discover  the  importance  of  copper  in  nutrition. 
Death  of  Charles  James  in  Boston. 

Death  of  Auer  von  Welsbach  at  Welsbach  Castle  in  Carinthia. 
Nils  Edlefsen,,  a  student  of  Ernest  O.  Lawrence,  constructs 

the  first  crude  cyclotron. 
H.  C.  Urey,  F.  G.  Brickwedde,  and  G.  M.  Murphy  discover 

the  hydrogen  isotope  of  mass  2. 

J.  Chadwick  and  M.  and  Mme.  Joliot-Curie  demonstrate  the 
existence  of  the  neutron,  which  W.  D.  Harkins  regards  as 
the  atom  of  an  element  "neuton"  of  atomic  number  zero. 
Colin  G.  Fink  and  P.  Deren  perfect  a  process  for  electroplating 

rhenium. 

M.  and  Mme.  Joliot-Curie  produce  artificial  radioactive  ele- 
ments by  a-ray  bombardment  of  light  elements. 
Death  of  Mme.  Curie. 

A.  V.  Grosse  liberates  metallic  protactinium. 
Death  of  N.  A.  Langlet, 
Death  of  Lord  Rutherford. 
Death  of  Georges  Urbain. 

Mile.  Marguerite  Perey  detects  element  87  (francium)  which 
is  formed  by  the  alpha-disintegration  of  a  small  percentage 
of  the  atoms  of  actinium. 

Hahn  and  Strassmann  split  the  nucleus  of  the  uranium  atom. 
C.  Perrier  and  E.  G.  Segre  discover  technetium  (element  43) 
among  the  fission  products  of  molybdenum  which  has  been 
bombarded  with  deuterons  in  the  Berkeley  cyclotron. 
Edwin  McMillan  and  Philip  Abelson  obtain  the  first  trans- 
uranium element,  neptunium  (element  93),  by  bombard- 
ment of  uranium  with  neutrons. 


898  DISCOVERY  OF  THE  ELEMENTS 

1940  D.  R.  Corson,  K.  R.  Mackenzie,  and  E.  G.  Segre  prepare 

element  85  (astatine)  by  bombarding  bismuth  with  helions. 
W.  Minder  and  Hulubei  and  Cauchois  independently  give 
evidence  for  the  existence  of  element  85  in  the  decay 
products  of  radon. 

1940  McMillan  and  Abelson  prepare  element  93  by  bombarding 

uranium  with  neutrons,  and  find  that  it  bears  a  closer 
resemblance  to  uranium  than  to  rhenium. 

1940  G.  T.  Seaborg,  Edwin  McMillan,  J.  W.  Kennedy,  and  A.  C. 

Wahl  prepare  plutonium  (element  94)  in  the  cyclotron. 

1941  The  Dow  Chemical  Company  produces  an  ingot  of  magnesium 

from  sea  water. 

Jan.  17,  1941        Death  of  Sven  Otto  Pettersson  at  Goteborg. 

Dec.  2,  1941         Death  of  Thomas  H.  Norton. 

1944-45  Americium  (element  95)  is  prepared  by  Seaborg,  R.  A.  James. 

L.  O.  Morgan,  and  A.  Chiorso;  curium  (element  96)  by 
Seaborg,  James,  and  A.  Ghiorso. 

1945  J.  A.  Marinsky,  L.  E.  Glendenin,  and  C.  D.  discover 

promethium  (element  61) . 

1950  S.  G.  Thompson,  A.  Ghiorso,  and  G.  T.  Seaborg  discover 

berkelium  (element  97).  S.  G.  Thompson,  K.  Street,  Jr., 
A.  Ghiorso,  and  G.  T.  Seaborg  discover  californium  (ele- 
ment 98). 

1954  Elements  99  and  100    (einsteinium  and  fermium)    are  an- 

nounced. 

1955  Mendelevium  (element  101)  is  announced  by  A.  Ghiorso,  B. 

G.  Harvey,  G.  R.  Choppin,  S.  G.  Thompson,  and  G.  T. 
Seaborg. 


Index 


Page  numbers  in  italics  indicate  portraits 


Abelson,  Philip,  868,  869 

Abildgaard,  Peder  Christian,  460 

Achard,  F.  C.,  417 

Acid  of  salt,  186,  187 

Acosta,  Joaquin,  422 

Actinide  series,  876-879 

Actinium  series,  820-824 

Afzelius,  Johan  Arvidsson,  313 

Afzelius,  Pehr,  346 

Agricola,  Georgius,  11  37,  98,  105,  677, 
755 

Agruss,  M.  G.,  820 

Alabaster,  505 

Albert  the  Great,  93,  186 

Alchemistic  symbols,  95 

Alchemists,  elements  of,  91;  paintings  of, 
91,  107,  120 

Aldrovandi,  Ulisse,  511,  512 

Allen,  William,  482,  741 

Alter,  David,  623,  624 

Alum,  588-608;  potash  in,  458,  459 

Aluminum,  588-610;  in  plants  and  ani- 
mals, 610;  isolation  of  by  Wohler,  598, 
600 

Alunite  (see  Alum) 

Amalgamation  process,  50,  51 

American  Philosophical  Society,  375,  400, 
403 

Americium,  874-876 

Ammonia,  190 

Ampere,  Andre-Marie,  741 

Animal  nutrition,  151,  152;  calcium  in, 
510;  carbon  in,  83 

Animals,  aluminum  in,  610;  barium  in, 
516,  517;  beryllium  in,  570;  boron  in, 
585,  586;  bromine  in,  755;  cerium  in, 
558;  copper  in,  28;  effect  of  thallium 
on,  641;  fluorine  in,  770;  hydrogen  in, 
187,  188;  iron  in,  38;  lithium  in,  489, 
490;  magnesium  in,  527,  528;  manga- 
nese in,  174;  potassium  in,  460;  silica 
in,  588;  sodium  in,  467,  468;  strontium 
in,  521;  sulfur  in,  57;  titanium  in,  549- 
551;  vanadium  in,  364 

Antimony,  95-103;  calcination  of,  97; 
early  uses  of,  103;  native,  103 

Antonoff,  G.  N.,  812 

Aqua  regia,  186 

Arfwedson,  Johan  August,  267,  485-488, 
494-503,  687,  701 

Argon,  784,  785 


Argyrodite,  688,  689 

Aristotle,  3 

Armstrong,  Eva,  403 

Arrhenius,   Carl  Axel,  495,  695,  697 

Arrhenius  Svante,  550 

Arsenic,     92-95;     investigation     of     by 

Brandt,  156;  isolation  of,  92;  metallic 

nature  of,  95 
Artificial  diamonds,  768 
Asphalt,  76-77 
Astatine,  865,  866 
Auer,    Carl,   Baron  von   Welsbach,   713, 

714,  715-717 
Azurite,  23 


Baas-Becking,  L.  G.  M.,  461 

Bagge,  C.,  465 

Bailey,  E.  H.  S.,  517 

Balard,   Antoine-Jerome,   733,   744,   747, 

749-754 

Balfour,  I.  B.,  246 
Balke,  C.  W.,  344 
Balloon  ascensions  by  Gay-Lussac  and 

Biot,  576,  577 
Bancroft,  H.  H.,  297,  398 
Banks,  Sir  Joseph,  201 
Barba,  Padre  Alvaro  Alonso,  10,  18,  45, 

50,  51,  106,  188,  293 
Barium,  510-517;  in  plants  and  animals, 

516,  517;  metallic,  516 
Baryta,  507,  514,  515 
Basalt,  sodium  in,  466,  467 
Baskerville,  Charles,  364 
Bauch,  Martin  Anders,  221 
Baume,  Antoine,  415 
Bayen,  Pierre,  212 
Beccari,  Jacopo  Bartolomeo,  514 
Beccaria,  Giovanni  Battista,  40 
Becher,  Johann  Joachim,  197, 199 
Beckmann,  Johann,  144,  160 
Becquerel,  Antoine-Henri,  803,  804 
Beddoes,  Thomas,  478,  479 
Bell,  Alexander  Graham,  318 
Berg,  Otto,  851,  852 
Bergman,  Torbern,   159,   164,  167,   169, 

223,  255-257,  260,  261,  286,  288,  304, 

326,  473,  515,  516,  522,  528,  544,  551; 

his  statement  on  sedative  salt,  575 
Berkelium,  876,  877 
Bernhardt,  Johann  Christian,  185 


899 


900 


DISCOVERY  OF  THE  ELEMENTS 


Berthelot,  Pierre-Eugene-Marcelin,  407, 
767 

Berthollet,  Claude-Louis,  286,  420,  421, 
433,  486,  729,  730,  734,  735 

Beryllium,  565-570;  first  preparation  of 
pure,  by  electrolytic  process,  569,  570; 
in  plants  and  animals,  570 

Berzelius,  Betty,  707 

Berzelius,  Jons  Jacob,  135,  171,  184,  302, 
306-315,  342,  349,  350,  353,  354,  357, 
358,  362,  376,  385,  386,  423,  431-434, 
438,  440,  444,  485-487,  497-499,  501, 
502  509,  510,  516,  533,  545,  549,  550, 
552-554,  556,  558-560,  675,  685,  783; 
his  friendship  with  Mosander,  700-706, 
707,  711;  his  friendship  with  Wb'hler, 
597,  598,  602;  his  work  with  silicon, 
586,  587 

Bible  elements  mentioned  in  the,  5-8, 
14-16,  19-22,  30-31,  41-43,  52,  53, 
76,  96,  183,  462,  464 

Bicquet,  Jean-Baptiste-Michel,  467 

Biot,  Jean-Baptiste,  his  balloon  ascension 
with  Gay-Lussac,  576,  577 

Biringuccio,  Vannoccio,  153,  154 

Bishop,  Joachim,  423 

Bismuth,  103-109,  157,  158;  recipes  for 
making  it,  107 

Bitumen,  76-77 

Bjorkbom,  Carl,  502 

Black,  Joseph,  205,  206,  237,  243,  456, 
523,  524 

Blake,  W.  P.,  305 

Bleaching,  with  chlorine,  734,  735 

Blomstrand,  C.  W.,  343 

Blood,  iron  in,  39;  red  color  of,  39 

Boerhaave,  Herman,  189,  192,  236,  237, 
456,  462,  466,  474 

Bottger,  Rudolph  Christian,  640,  646 

Bohn,  Johann,  473,  474 

Bohr,  Niels,  849 

Bolivar,  Simon,  423 

Bologna  stone,  510-515 

Bolton,  Werner  von,  344 

Boltwood,  Bertram  Borden,  813 

Boracite,  583 

Borax,  570-580;  early  process  of  recover- 
ing, 584;  in  California,  583,  584 

Borch,  Ole,  211 

Boric  acid,  decomposition  of  by  Gay- 
Lussac  and  Thenard,  579,  580;  in  sea 
water,  584,  585;  natural,  581-583 

Boron,  570-586;  Davy's  method  of  isolat- 
ing, 580;  in  plants  and  animals,  585, 
586 

Born,  Baron  Ignaz  Edler  von,  264,  290, 
321,  322,  323,  326,  632 


Bostock,  John,  370,  383 
Boulduc,  Gilles-Egide-Frangois,  522 
Bourdelin,  Louis-Claude,  574 
Boussingault,  Jean-Baptiste,  86,  187,  422, 

423 

Bowen,  George,  489 
Boyle,  Robert,  4,  112,  114,  122,  123,  12o, 

126,  188,  197,  198 

Brand,  Hennig,  108,  109,  121-124;  proc- 
ess of  making  phosphorus,  126 
Brande,  William  Thomas,  371,  428,  437, 

439,  487 
Brandes,  R.,  745 

Brandt,  Georg,  156-160,  476,  671 
Brass,  19,  141,  142 

Brauner,  Bohuslav,  660,  661,  716,  717 
Braunstein   (see  Pyrolusite) 
Breislak,  Abbe  Scipione,  590 
Brewster,  Sir  David,  622,  623 
Brodie,  Sir  Benjamin,  385 
Bromide  mineral,  754,  755 
Bromine,  747-755;  from  sea  water,  754; 

in  animals,  755 
Bronze,  43 
Brooke,  H.  J.,  502 

Brooks,  Harriet  (see  Pitcher,  Mrs.  Frank) 
Brown,  Samuel,  193 
Browne,  C.  A.,  387 
Brownrigg,  William,  83,  214,  409,  412- 

415,  462 

Bruce,  Archibald,  150 
Bunge,  G.,  467 
Bunsen,  Robert  Wilhelm,  488-490,  615, 

624-629,  632-634 
Bussy,     Antoine-Alexandre-Brutus,     526, 

557,  569 
Butlerov,    Alexander    Mikhailovich,    445, 

446 


Cabezas,  Joaquiri,  420 

Cadmium,  529-535;  from  zinc  ores,  534, 

535 

Cady,  Hamilton  P.,  791 
Cailliaud,  F.,  565 
Calamine,  147-149 
Calcium,  505-510;  in  plant  and  animal 

nutrition,  510 
Caley,  Earle  R.,  47,  264 
California,  borax  in,  583,  584 
California  gold  rush,  13 
Californium,  876,  877 
Calomel,  52 

Cap,  Paul-Antoine,  102 
Carbon,   58,   75;   as  an  element,   59;   in 

plant  and  animal  nutrition,  83-87 
Carbon  dioxide,  237,  238 


INDEX 


901 


Cardano,  Girolamo,  408 

Carstanjen,  E.,  641 

Carter,  Howard,  506 

Casciarolo,  Vincenzo,  510 

Cassiterite,  43 

Cathcart,  Charles  Murray,  535 

Cavendish,    Henry,   200-204,    208,    214, 

235,  238,  380,  779 
Caycedo,  Bernardo  J.,  290,  299 
Celli,  Marco  Antonio,  511 
Ceria,  699 
Cerium,  551-558;  in  plants  and  animals, 

558 

Cesium,  626-631 
Chabaneau,    Pierre-Frangois,    289,    417- 

420 

Chadwick,  James,  836 
Chameleon  mineral,  172,  173 
Chaptal,  Jean-Antoine-Claude,  294,  295, 

382,  739 
Charlotte,  Elisabeth,  her  character  sketch 

of  Homberg,  573 

Chenevix,  Richard,  382,  383,  430,  431 
Chevillot,  Pierre-Frangois,  173 
Chevreul,  Michel-Eugene,  173,  383,  384 
Children,  J.  G.,  534 
Chilean  nitrate,  193 
Chile,  selenium  in,  315 
Chinese,  as  originators  of  large-scale  zinc 
production,    142-144;   in  discovery   of 
oxygen,  209;  knowledge  of  arsenic  pos- 
sessed by,  92-94;  salt  industry,  461 
Chlorine,  729-736;  bleaching  with,  734, 
735;  disinfecting  with,  735;  in  the  hu- 
man body,  736 
Choke  damp,  83 
Choppin,  G.  R.,  879 
Christison,  Sir  R.,  246 
Chromite,  278,  279 
Chromium,  270-279,  394;  in  meteorites, 

279;  in  the  emerald  and  ruby,  278 
Chronology,  886-898 
Chrysoberyl,  Arfwedson's  analysis  of,  500 
Cinnabar,  47-49 
Clarke,  Edward  Daniel,    171,   263,  485, 

486,  534,  558 
Clayton,  Reverend  John,  81 
Clement,  Nicolas,  738,  740 
Cleve,  Per  Teodor,  709-712,  789,  790 
Cloud,  Joseph,  430,  431 
Coal,  75;  description  of,  75;  in  Pennsyl- 
vania, 75 
Coal  gas,  81 

Cobalt,  152-161;  discoverer  of,  156;  ele- 
mental nature  of,  159;  in  meteorites, 
160,  161;  in  nutrition,  161;  metallic, 


accurate   description   of,   157,   roasted, 
153 

Cock,  Thomas,  426 

Coindet,  Jean-Frangois,  742-744 

Coleridge,  Samuel  Taylor,  473 

Colin,  Jean-Jac<jues,  744 

Collet-Descotils,  H.-V.,  394,  437 

Columbite,  375-380 

Columbium  (see  Niobium) 

Columbus,  Christopher,  9,  22 

Combes,  A.,  482 

Combustion,  doctrine  of,  228 

Condorcet,  M.-J.-A.-N.  de  Caritat,  his 
eulogy  on  Marggraf,  591,  592 

Conti,  Prince  Piero  Ginori,  582,  583 

Conybeare,  Reverend  J.  J.,  386 

Copley  Medal,  83 

Copper,  19-29,  141,  142;  in  plants  and 
animals,  28;  in  spring  waters,  25 

Copper  mines,  26 

Cornwall,  H.  B.,  647 

Corrosive  sublimate,  52 

Corson,  D.  R.,  865 

Cortenovis,  Father  Angelo  Maria,  407 

Coryell,  Charles  D.,  864 

Coster,  Dirk,  850 

Courtois,  Bernard,  192,  736-740 

Courtois,  Jean-Baptiste,  192 

Cramer,  Johann  Andreas,  109,  146-148 

Crampton,  C.  A.,  585 

Cranston,  John  A.,  820,  821 

Crawford,  Adair,  517,  518 

Crell,  Lorenz  von,  133,  134,  528,  551 

Cronstedt,  Axel  Fredrik,  161,  163-165, 
416,  417,  551,  553 

Crookes,  Sir  William,  316,  635-637,  638, 
639,  811;  discoveries  in  radioactivity, 
molecular  physics,  uranium  Xi,  637; 
inventor  of  radiometer  and  spinthari- 
scope, 637 

Crookesite,  316,  641 

Crowe,  James  M.,  879 

Cryolite,  608-610 

Cunningham,  B.  B.,  872,  875 

Curie-Joliot,  Irene  (see  Joliot,  Irene 
Curie) 

Curie,  Marie  Sklodowska,  560,  802-811, 
813,  829,  830 

Curie,  Pierre,  802-811,  813,  829 

Curium,  874-876 

Cyclotron,  860 

Dains,  Frank  Burnett,  403,  609 

Dalton,  John,  399 

da  Vinci,  Leonardo,  91,  209,  210 


902 


DISCOVERY  OF  THE  ELEMENTS 


Davy,  Sir  Humphry,  55,  202,  276,  370, 

472,  478-484,  487,  498,  507-510,  545, 

730    732—734 
de  Acosta,  Father  Jose,  10,  17,  49,  108; 

his  description  of  Peruvian  emeralds, 

566 
de  Andrada  e  Silva,  Joze  Bonifacio,  484, 

485 

de  Beaumont,  Louis-Leonce  Elie,  60S 
Debierne,  Andre,  813 
de  Blancourt,  Haudicquer,  154,  455 
de  Boisbaudran,  Paul-Emile  Lecoq,  671, 

672-676,  712,  717 
de  Bourdelin,  Louis-Claude,  456 
Debray,  J.  Henri,  446 
Debus,  Heinrich,  625 
de  Carvalho,  M.  Herculano,  270 
de  Castro,  Giovanni,  589 
de    Chancourtois,    Alexandre-Emile    Be- 

guyer,  654-656 
de  Condorcet,  Marquis,  475 
de  Elhuyar,  Fausto,  255,  256,  257,  284, 

285-298,  299,  391,  392,  418 
de  Elhuyar,  Juan  Jose,  255-257,  285-299, 

391,  418,  551 

de  Figueiredo  Neiva,  Venancio,  485 
de  Fontenelle,  B.  Le  Bovier,  99,  102,  513; 

his  eulogy  of  Homberg,  573,  574 
de  Fourcroy,  A.-F.,  271,  273,  276,  279, 

341,  382,  394,  458-460,  515,  567 
de  Galvez-Canero,  A.,  297,  299,  403 
Deherain,  Pierre-Paul,  467 
Delafontaine,  Marc,  705,  712 
de  Larderel,  Francesco  Giacomo,  582 
de  Leon,  Joaquin  Velazquez,  402 
del  Rio,  Andres  Manuel,  254,  292,  293, 

299,  316,  352,  359,  391-405,  434;  re- 
garding iodine  as  a  mineral,  745,  746 
de  Mayerne,  Turquet,  200 
de  Medina,  Bartolome,  291,  293 
de  Menonville,  N.-J.  Thiery,  411 
Demargay,  Eugene-Anatole,  717,  718-720 
de  Marignac,  Jean^Charles  Galissard,  70S 
de  Morveau,  Louis-Bernard  Guyton,  185, 

192,  258,  544,  735 
de  Respour,  P.  M.,  147 
Derham,  W.,  511 
Desgrez,  Alexandre,  490 
Desormes,  Charles-Bernard,  738,  740 
de  Tournefort,  J.-P.,  524,  590 
de  Ulloa,  Antonio,  406,  409^12,  420,  423 
Deuterium,  205 
de  Velazquez  Cardenas  y  Le6n,  Joaquin, 

289,  299 

de  Viera  y  Clavijo,  Father  Jose,  218 
Deville  (see  Sainte-Claire  Deville) 


Diamonds,  60;  artificial,  768 

Didymia,  699-705 

Digitalis,  516 

Disinfecting,  with  chlorine,  735 

Dobereiner,  Johann  Wolfgang,  519,  653, 

654 

Domeyko,  Ignaz,  315 
Dorn,  Friedrich  Ernest,  814 
Dossie,  Robert,  186,  189 
Draper,  John  W.,  786 
Duhamel  du  Monceau,  Henri-Louis,  474 
Dumas,    Jean-Baptiste- Andre,    187,    639, 

640,  742 

Dumoulin,  G.,  462 
Dwight,  Timothy,  463 
Dysprosia,  717 

Edwards,  William  Frederic,  173 

Eggertz,  Hans  Peter,  184,  309,  310 

Egyptians,  sal  ammoniac  preparation  of, 
188,  189 

Einsteinium,  878,  879 

Ekeberg,  Anders  Gustaf,  307,  345-350 

Element,  conception  of,  3;  first  man  to 
discover,  109 

Elements,  Lavoisier's  list  of,  477;  men- 
tioned in  the  Bible,  5-8,  14-16,  19-22, 
30,  31,  41-43,  52,  53,  76,  96,  183,  462, 
464;  modern  list,  884,  885;  of  the  al- 
chemists, 91 

Elsholtz,  Johann  Sigismund,  755,  757 

Elster,  Julius,  818,  831 

Emerald,  chromium  in  the,  278 

Epsom  salt,  521,  522 

Erbia,  705-712 

Erythronium,  353,  394 

Esmark,  Jens,  558 

Esmark,  Reverend  Hans  Morten  Thrane, 
559 

Estner,  Abbe  Franz  Joseph  Anton,  327, 
329,  331-333 

Europia,  717-720 

Euxenite,  677,  680;  discovery  of,  678 

Eye  paints,  ancient,  96 

Fages  y  Virgili,  Juan,  288,  289,  420 

Fafans,  Kasimir,  811,  812,  820 

Fajardo,  Clavijo,  420 

Fang,  Lien-Che  Tu,  461 

Faulkner,  Thomas,  386 

Ferber,  J.  J,,  459 

Fermi,  Enrico,  860,  861,  867,  868 

Fermium,  878,  879 

Fiala,  Frantisek,  336 

Fink,  Colin  G.,  13 

Fire  damp,  83 


INDEX 


903 


Fittig.  Rudolf,  782 

Flame  test,  for  lithium,  516 

Fleck,  Sir  Alexander,  825,  827 

Flink,  Gustaf,  488 

Fluorescent  lighting,  535 

Fluorine,  755-770;  in  plants  and  animals, 

770 

Fluorine  gas,  victims  of,  762,  763 
Forbes,  Allyn  B.,  987 
Forchhammer,    Johan    Georg,    161,    517, 

584,  585 

Forster,  Georg,  323 
Fourcroy,  Antoine-Frangois  ( see  de  Four- 

croy) 

Francium,  866,  867 
Frankland,  Edward,  786 
Franklin,  Benjamin,  214,  415 
Franklinite,  151 
Frasch,  Herman,   56;   process   of  mining 

Louisiana  sulfur,  464 
Fraunhofer,  Joseph,  620 
Fremy,  Edmond,  763 
Friedrich,  Duke  Johann,  122,  123,  124 
Fuchs,  Johann  Nepomuk  von,  485 
Fyfe,  Andrew,  743 

Gadolin,  Johan,  696,  698,  699 

Gadolinia,  712,  713 

Gadolinite,  696 

Gahn,  D.  Heinrich,  134 

Gahn,  Johan  Gottlieb,  133,  134,  136,  137, 

168,  169-172,  184,  223,  260,  309-311, 

313,  458,  514,  515,  556 
Gallium,  671-677 
Garbett,  Samuel,  186 
Gas  fixtures,  82 

Gas  lighter,  automatic,  715,  716 
Gas  lighting,  81-82 
Gaultier,  Henri-Frangois,  744 
Gay-Lussac,  Louis-Joseph,  482,  496,  575- 

580,  730,  732,  733,  744;  his  balloon 

ascension  with  Biot,  576,  577  ' 
Geiger,  Hans,  826 
Geitel,  Hans  F.  K.,  818,  831 
Genth,  F.  A.,  305 
Geoffroy,  Claude-Frangois,  108 
Geoffroy,    Claude-Joseph    (Geoffroy   the 

Younger),  36,  188,  382 
Geoffroy,  Etienne-Frangois  (Geoffroy  the 

Elder),  12,  24,  25,  36,  77,  168,  189, 

191,  192,  464,  589 
Germanite,  677,  690 
Germanium,  683-690 
Gesner,  Johann  Albrecht,  160 
Ghiorso,  A.,  876,  879 


Gibbes,  Lewis  Reeve,  664-667,  synopticnl 
table  of,  665 

Giesel,  Friedrich  O.,  823 

Gilbert,  L.  W.,  534 

Glass,  465,  466,  586-588;  etching,  756. 
760;  gold  ruby,  11;  Macquer's  account 
of  etching,  760,  761;  pyrolusite  in 
manufacture  of,  168 

Glassmaking,  use  of  cobalt  in,  153 

Glauber,  Johann  Rudolph,  12,  144,  172, 
183,  184,  186,  190,  466,  523 

Glauber's  salt,  183,  466 

Glendenin,  L.  E.,  864 

Glueck,  Rabbi  Nelson,  21 

Gmelin,  C.  G.,  487 

Gmelin,  Johann  Friedrich,  568 

Gmelin,  Leopold,  597 

Godfrey,  Ambrose  (see  Hanckwitz,  Am- 
brose Godfrey) 

Godlewski,  Tadeusz,  823 

Gohring,  O.  H.,  811 

Goethe,  J.  W.  von,  514,  549,  596,  745 

Gold,  6;  in  California,  13;  in  sea  water, 
13;  potable,  12;  ruby  glass,  11 

Gore,  George,  764 

Gray,  Daniel,  648 

Greenockite,  535 

Green  Vitriol,  33 

Gregor,  Reverend  William,  545-548 

Gren,  F.  C.,  258,  382 

Grew,  Nehemiah,  521 

Grill,  Johan  Abraham,  571 

Grosse,  Aristid  V.,  820-822,  848 

Guericke,  Otto  von,  114,  571 

Guettard,  Jean-£tienne,  462 

Gunther,  R.  T.,  264 

Hafnium,  848-851 

Hahn,  Otto.  812,  820,  823-826,  867,  868 

Haidinger,  Karl,  327 

Hales,  Stephen,  212,  238,  241 

Half-metals,  157,  163 

Hall,  Charles  Martin,  606,  607 

Hall,  Sir  James,  382 

Hamburger,  L.,  560 

Hampe,  Dr.  J.  H.,  129,  130 

Hanckwitz,  Ambrose  Godfrey,  113,  114, 

128 

Hare,  Robert,  423,  424 
Harvey,  B.  G.,  879 
Hasselqvist,  Fredrik,  189 
Hatchett,  Charles,  264,  338-343,  368-389 
Hausmann,  Johann  Friedrich,  356 
Haiiy,  Rene-Just,  485,  488,  498,  564,  566, 

567 

Haworth,  E.,  791 
Hayyan,  Abu  Musa  Jabir  ibn,  188 


904 


DISCOVERY  OF  THE  ELEMENTS 


Helium,  785-792;  discovery  of,  637 

Hellot,  Jean,  108,  114 

Helmholtz,  Hermann  (Ludwig  Ferdinand) 

von,  634 

Helmont,  Jan  Baptist  van,  206,  207 
Hematite,  33 
Henckel,  J.  F.,  147,  149 
Henry,  Thomas,  526,  528,  735 
Henry,  William,  731 
Henze,  M.,  364 
HeracKtus,  4 
Herapath,  William,  534 
Hermann,  K.  S.  L.,  532 
Hermbstadt,  Sigismund  Friedrich,  224 
Heroult,  Louis-Toussaint,  606,  608 
Hess,  Gertrude  D.,  375,  387 
Hevesy,  Georg  von,  849-851 
Hewson,  William,  40 
Heyrovsky,  Jaroslav,  853-855 
Hiarne,  Urban,  162 
HiUebrand,   William    Francis,   555,   557, 

787,  788 

Hirsch,  Alcan,  557 
Hisinger,  WiUielm,  313,  485,  497,  502, 

551-554,  555,  557 
Hjelm,  Peter  Jacob,  171,  172,  261-264, 

551 

Hofer,  Hubert  Franz,  581 
Honigschmid,  Otto,  817 
Hoffmann,  Friedrich,  75,  474,  522 
Hofmann,  August  Wilhelm  von,  635,  636 
Holmia,  709-712,  717 
Homberg,  Willem,  36,  112,  513,  571-574; 

character  sketch  of,  573 
Home,  Sir  Everard,  370 
Hooke,  Robert,  210 
Hope,  John,  244?  245 
Hope,    Thomas    Charles,    504,    518-521, 

741 

Hopkins,  B.  Smith,  724 
Howard,  Edward,  382 
Howe,  James  Lewis,  418 
Human  body,  chlorine  in  the,  736 
Humboldt,    Baron   Alexander   von,    293, 

294,  298,  360,  390,  391,  394,  396,  422, 

428 

Hunter,  M.  A.,  550 
Hussak,  Eugen,  431 

Hydrochloric  acid,  186,  187;  in  the  stom- 
ach, 187 
Hydrogen,  183-188,  197-205;  density  of, 

780,  781;  in  plants  and  animals,  187, 

188 

Ilsemann.  J.  C.,  171 
Incandescent  gas  mantle,  714,  715 


Indium  641-648;  commercial  develop- 
ment of,  647,  648;  description  of  first 
metallic,  645,  646;  detection  of  in  zinc 
blendes,  647 

Ingenhousz,  Jan,  74,  85,  86 

Iodide  mineral,  745,  746 

Iodine,  736-747;  in  spring  water,  744, 
745;  diffusion  of  in  nature,  746,  747 

Iridium,  436-440 

Iron,  in  animals,  38;  in  the  blood,  39;  in 
vegetable  ash,  36;  meteoric,  32;  mines, 
35;  seventeenth  century  symbol,  15; 
smelted,  33 

Jackson,  C.  T.,  305 

James,  Charles,  721,  722,  723 

Janssen,  Pierre- Jules-XHesar,  785,  786 

Jeanety,  M.,  420 

Jewett,  Frank  Fanning,  604 

John,  Johann  Friedrich,  496 

Johnson,  Percival  Norton,  426,  431,  432 

Johnston,  James  Finlay  Weir,  his  descrip- 
tion of  Berzelius  and  his  laboratory, 
559,  560 

Joliot,  Jean-Frederic,  834-838 

Joliot,  Mme.  Irene  Curie,  830,  831,  832- 
838 

Joss,  J.  R.,  754 

Juan  y  Santacilia,  Jorge,  409,  410 

Jungfleisch,  Emile-Clement,  674,  675 

Kaim,  Ignatius  Gottfried,  168 

Kalrn,  Per,  462,  525,  526 

Karsten,  C.,  532 

Kennedy,  Robert,  459,  460,  466,  467 

Kersten,  Carl,  317 

Kircher,  Father  Athanasius,  512 

Kirchoff,  Gustav  Robert,  490,  624,  626, 

627,  628,  629,  632 
Kirwan,  Richard,  520 
Kitaibel,  Paul,  305,  320,  826-336,  735 
Klaproth,  Martin  Heinrich,  258,  262,  263- 

267,  276,  277,  285,  S04,  305,  313,  326- 

336,  407,  459,  460,  467,  500,  542-544, 

548,  549,  566,  567,  632 
Klaus,  Karl  Karlovich,  440,  441-447 
Kopp,  Hermann,  186,  474 
Krafft,  Johann  Daniel,  116,  122-125 
Krypton,  792,  793 
Kunckel,  Johann  ( see  Lowenstera,  Johann 

Kunckel  von) 
Kupfernickel,  162,  163,  164 

Lac,  382 

Lampadius,  Wilhelm  August,  254 
Lamy,  Claude-Auguste,  638,  639,  640 
Lanthana,  699-705 


INDEX 


905 


Larson,  Mary,  427 
Lane,  Max  von,  846,  847 
Laugier,  Andre,  279 
Lava,  sodium  in,  466,  467 
Lavoisier,   Antoine-Laurent,   5,  55,   192, 
196,  225-257,  243,  244,  294,  457,  476, 
507;  his  list  of  elements,  477 
Lawrence,  Ernest  O.,  858,  860 
Lawson,  Isaac,  148 

Lead,  41;  resemblance  to  bismuth,  108 
Lead  mines,  42 
Lebeau,  P.,  569 
Leblanc,  Nicholas,  465 
Leclerc,  Georges-Louis,  435 
Lely,  D.,  Jr.,  560 

Lehmann,  Johann  Gottlob,  253,  272 
Leibniz,  Gottfried  Wilhelm,  121-123,  124 
Lemery,  Louis,  36-38,  190 
Lemery,  Nicolas,  13,  38,  45,  99,  100,  102, 
103,  106,  1073  126,  198,  200,  512,  513 
Lentilius,  Rosinus,  75 
Lenz,  Johann  Georg,  327 
Lepape,  A.,  796,  797 
Lepidolite,  487,  631,  632 
Leucite,  analysis  of  by  Arfwedson,  495; 

potash  in,  459 
Levy,  Armand,  151 
Lewis,  William,  417,  422,  527,  528 
Liebig,  Justus  von,  599,  600,  753 
Li  Jung,  461 
Lime,  507 

Linck,  Johann  Heinrich,  131,  162 
Linnaeite,  160 
Linne,  Carl  von,  26,  159 
Li-Ping,  461 

Lippmann,  Edmund  Oskar  von,  104,  407 
Lippmann,  Gabriel,  805 
Lithium,    484-490;    discoverer    of,    485; 
in  natural  waters,  489;  in  plants  and 
animals,  489,  490 
Liubarskii,  V.  V.,  428 
Lockyer,   Sir  Joseph  Norman,  637,  786, 

788,  789 

Lodestone  (Magnetite),  33 
Lomonosov,  M.  V.,  210 
Louisiana,  sulfur  in,  56 
Louyet,  Paulin,  760 
Lovits,  Tovii,  Egorovich,  277-279 
Lowenstern,    Johann    Kunckel    von,    12, 
110,  111,  154,  190;  experiments  of,  112 
Lowig,  Garl,  747,  748,  750 
Lowitz,  Tobias  (see  Lovits,  Tovii  Egoro- 
vich) 

Lucas,  Alfred,  407 
Lucas,  Anthony  F.,  79 
Lulio,  Raimundo,  190 
Lumb,  A.  D.,  423 


Lutetia,  720-724 

McCollum,  E.  V.,  528 

McCoy,  Herbert  Newby,  714 

McCutcheon,  F.  G.,  676 

McFarland,  D.  F.,  791 

Mackenzie,  K.  R.,  865 

McMillan,  Edwin  M.,  868,  869-871,  872 

MacNeven,  William  James,  481 

McPherson,  William,  663 

Macquer,  Pierre-Joseph,  60,  114,  130, 
185,  187,  190,  457,  570,  571 

Madacs,  Petrus,  159 

Magdeburg  miracles,  571,  572 

Magini,  Giovanni  Antonio,  511 

Magnesium,  521-528;  from  sea  water, 
528;  in  plants  and  animals,  527 

Magnetite  (Lodestone),  33 

Magnus,  Albertus  (see  Albert  the  Great) 

Magnus,  Gustav,  808 

Malachite,  23 

Malpighi,  Marcello,  521 

Manganese,  168-174;  discoverer  of,  168; 
in  animals,  174;  in  plants,  ITS,  174; 
metallic,  169 

Mao-Kh6a,  209,  210 

Marcet,  Alexandre,  812,  350,  386,  425, 

433,  434,  438,  487,  496 
Marden,  J.  W.,  363 

Marggraf,  Andreas  Sigismund,  132,  140, 
148,  149,  456,  476,  514,  523-525,  591, 
592,  619,  756 
Marinsky,  J.  A.,  864 
Marsden,  E.,  827 
Mascagni,  Paolo,  581,  582 
Matches,  phosphorus,  135,  136 
Matthiessen,  A.,  488 
Maxson,  R.  N.,  193 
Mayow,  John,  210,  212,  244 
Meerschaum,  526 
Meggers,  William  Frederick,  854 
Meionite,  analysis  of  by  Arfwedson,  495 
Meissner,  W.,  532 
Meitner,  Lise,  812,  820,  868 
Mendeleev,  Dmitri  Ivanovich,  653,  657, 
660-665,  688,  689;  elements  predicted 
by,  663;  periodic  table  of  the  elements 
of,  652,  670 
Mendelevium,  878,  879 
Mendez,  Dr.,  522 
Menghini,  Vincenzo,  39 
Menschutkin,  B.  N.,  428 
Mephitic  air,  241,  242 
Mercury,  47;  freezing  of,  52 
Metals,  ancient,  5;  Swedish,  152-174 
Meteorites,  chromium  in,  279;  cobalt  in, 
160,  161;  nickel  in,  165,  166 


906 


DISCOVERY  OF  THE  ELEMENTS 


Meunier,  J.,  490 

Mexico,  first  ironworks  in,  396 

Meyer,  J.  K.  F.,  133,  165 

Meyer,  Julius  Lothar,  653,  657,  658-661 

Meyer,  Kirstine,  595 

Miller,  C.  F.,  490 

Mine  accidents,  frequent  causes  of,  83 

Mineral,  iodide,  745,  746 

Mineral  waters,  uranium  in,  270 

Mineralogy,  chemical  system  of,  165 

Mines,    ancient    silver,    16;    copper,    26; 

iron,  35;  lead,  42;  nickel,   166  Potosi, 

17;  zinc,  150 
Mitchill,  Samuel  Latham,  374,  375,  421, 

506 
Moissan,  Ferdinand-Frederic-Henri,  343, 

550,  764-766,  768,  769,  770 
Moles,  Enrique,  288,  392,  393,  394,  403 
Molybdenum,  258-264 
Molybdic  acid,  369 
Monnet,  Antoine-Grimoald,  458,  459 
Mosander,  Carl  Gustav,  556,  699,  700- 

706 

Moseley,  Henry  Gwyn  Jeffreys,  844-S4S 
Moureu,  Charles,  796,  797 
Mudge,  B.  F.,  464 
Miiller,  Franz  Joseph,  Baron  von  Reieh- 

enstein,  303-305,  325-327,  548 
Miinchausen,  Baron  von,  257 
Murray,  William  S.,  647 
Musin-Pushkin,  Apollos  Apollo sovich,  277, 

278,  426 

Mutis,  Jose  Celestino,  289,  419,  423 
Muwaffaq,  Abu  Mansur,  506 

Nagy,  Julius,  336 

Nasini,  Raffaello,  572,  790 

Natural  gas,  79-81 

Natural  soda,  464,  465 

Natural  waters,  lithium  in,  489 

Nature,  diffusion  of  iodine  in,  746,  747 

Neodymia,  713-717 

Neptunium,  868-870 

Neri,  Father  Antonio,  154 

Neumann,  Caspar,  107,  145,  146,  508, 
522;  on  alum,  590 

Newlands,  John  Alexander  Reina,  656, 
657,  683 

Niccolite,  163,  164 

Nicholson,  William,  164,  382 

Nickel,  161-167;  accepting  the  new  ele- 
ment, 164,  165;  discoverer  of,.  161; 
early  alloys,  166,  167;  famous  mines 
and  smelters,  166;  first  pure  malleable, 
167;  history  of,  162;  in  meteorites,  165, 
166 

Nilson,  Lars  Fredrik,  550,  677-683 


Niobium,  339-345;  discovery  of,  371 

Niter,  190-193 

Nitric  acid,  184,  185 

Nitrogen,  205-208;  as  distinct  from  car- 
bon dioxide,  238;  compounds,  188-193; 
discoverer  of,  235:  elementary  nature 
of,  208 

Nobel  Prize,  awarded  to  Chadwick,  836; 
to  Mme.  Curie,  830;  to  the  Curies,  829; 
to  Fermi,  861;  to  Hahn,  812,  867;  to 
von  Hevesy,  849;  to  Joliot-Curies,  837; 
to  von  Laue,  847;  to  Lawrence,  860;  to 
Seaborg  and  McMillan,  870;  to  Soddy, 
825 

Noddack,  Walter,  851-853 

Nollet,  Abbe  Jean-Antoine,  130,  513 

Nordenskiold,  Baron  Nils  Adolf  Erik,  316, 
346,  347,  516,  533,  552,  641 

Norton,  Thomas  H.,  556,  557 

Nutrition,  cobalt  in,  161 

Nuttall,  Thomas,  489 

Ocher,  33 

Oersted,  Hans  Christian,  592,  594,  595 

Oesper,  Ralph  E.,  465 

Oil  of  vitriol,  185,  186 

Oppenheimer,  J.   Robert,   858 

Orfila,  Mateo-Jose-Ruenaventura,  276 
277,  295 

Osann,  G.  W.,  440 

Osmium,  43$-440 

Ostwald,  Wilhelm,  visit  to  Curie  labora- 
tory, 811 

Owens,  R.  B.,  826 

Oxides  of  manganese,  Arfwedson's  re- 
search on,  495,  496 

Oxygen,  208-229;  density  of,  780,  781 

Paints,  ancient  eye,  96 

Palcani,  Luigi,  465 

Palissy,  Bernard,  154,  155 

Palladium,  429-432;  discoverer  of,  171 

Pallas,  Peter  Simon,  272-274 

Paneth,  F.  A.,  862 

Paracelsus,  105,  144,  153,  197 

Patronite,  364 

Pauli,  Matthaus,  his  glass-etching  fluid, 

756 

Pedanios,  Dioscorides,  455 
Peligot,  Eugene-Melchior,  267,  268,  269, 

270,  501 
Pelletier,  Bertrand,  264,  416,  420,  421, 

516 

Penaflorida,  Count  of,  285 
Pennsylvania,  coal  discovery  in,  75 
Perdix,  Bartholomew,  589 


INDEX 


907 


Pereira-Forjas,  A.,  270 

Perey,  Marguerite,  866 

Periodic  law,  discovery  of,  653-669 

Periodic  table  of  the  elements,  Mende- 
leev's, 652;  Meyer's,  659 

Perkaan,  L,  875 

Peroni,  G.,  490 

Perrier,  C.,  862 

Petalite,  485-489;  Arfwedson's  work  on, 
496,  497 

Petroleum,  77-79 

Petroleum  well,  the  first  U.  S.,  79 

Petrov,  Vasilii  Vladimirovich,  228,  229 

Pettersson,  Sven  Otto,  550,  677,  679,  680 

Pharmacopoeia,  Schroeder's,  94,  101 

Phelps,  Almira  Hart  Lincoln,  SO 

Phlogiston,  197,  206,  212,  227,  242 

Phosphorus,  109-116;  chemical  nature, 
incorrect  views  of,  130,  131;  constitu- 
ent of  bone,  133;  description  of  Brand's 
process  of  making,  126;  discovery  of, 
121;  elemental,  discoverer  of,  121; 
Hanckwitz's  recipe  for,  129;  matches, 
135;  new  method  of  preparation,  132; 
preparation  of,  from  vegetable  and  ani- 
mal matter,  133;  presence  of,  132,  133; 
rediscovery  of,  125;  red  modification  of, 
135;  secret  processes  of  making,  112, 
114 

Pisani,  Felix,  631 

Pitchblende,  266-270 

Pitcher,  Mrs.  Frank,  815 

Plant  nutrition,  calcium  in,  510;  carbon 
in,  83-87;  zinc  in,  151,  152 

Plants,  aluminum  in,  610;  barium  in, 
516,  517;  beryllium  in,  570;  boron  in, 
585,  586;  cerium  in,  558;  copper  in, 
28;  effect  of  thallium  on,  641;  fluorine 
in,  770;  hydrogen  in,  187,  188;  lithium 
in,  489,  490;  magnesium  in,  527,  528; 
manganese  in,  173;  origin  of  potash  in, 
456-458;  silica  in,  588;  sodium  in,  467, 
468,  strontium  in,  521;  sulfur  in,  57; 
titanium  in,  549-551;  vanadium  in,  364 

Plaster  of  Paris,  506 

Platinum,  407-429 

Plattner,  Carl  Friedrich,  630 

Pliny  the  Elder,  8,  9,  141,  407,  465,  565 

Pliny  the  Younger,  466 

Poda,  Abbe  Nicolaus,  631 

Poincare,  Henri,  805 

Polo,  Marco,  77,  141 

Polonium,  806—809;  a  non-radioactive  iso- 
tope of,  809 

Pomet,  Pierre,  155,  156 

Pontin,  M.  M.  af,  509,  510 


Potash,  from  vegetable  ash,  455;  in  alum, 

458,  459;   in  leucite,  459;  in  pumice, 

459,  460;  origin  in  plants,  456-458 
Potassium,  473-484;  in  animals,  460 
Potassium  permanganate,  172,  173 
Potosi  mines,  17 

Pott,  J.  H.,  169,  173,  457,  590 

Praseodymia,  713-717 

Priestley,  Joseph,  40,  83-85,  208,  213- 
215,  216-221,  238-240,  242,  423;  his 
apparatus,  217;  his  laboratory,  219 

Promethium,  863-865 

Proust,  Joseph-Louis,  165,  286,  291,  420 

Prout,  William,  182,  187;  regarding  io- 
dine, 741,  742 

Pseudo-Geber,  184-^186 

Pumice,  potash  in,  459,  460 

Pumping  engine,  del  Bio's,  396 

Pyrite,  33;  thallium  in,  641 

Pyroligneous  acid,  183,  184 

Pyrolusite,  168,  170-173 

Quartz,  586-588 

Quennessen,  Louis,  418 

Qvist,  Bengt  (Andersson),  259,  260 

Radioactivity,  artificial,  831-8S8 
Radium,  809-811 
Radium  series,  &13-820 
Ramacsahazy,  Colonel  Joseph,  324 
Rammelsberg,  Carl  Friedrich,  361 
Ramsay,  Sir  William,  242,  637,  778,  781- 

785,  788,  792,  793-796 
Raspe,  Rudolf  Erich,  257 
Rayleigh,   Lord,   the   Third    (see    Strutt, 

John  William ) 
Regnault,  Henri-Victor,  662 
Reich,  Ferdinand,  254,  641,  642,  643-646 
Remsen,  Ira,  783 
Retzius,  Anders  Jahan,  222 
Rey,  Jean,  210 
Rheinboldt,  Heinrich,  593 
Rhenium,  851-855 

Rhodium,  432-436;  discoverer  of,  171 
Rich,  M.  N.,  363 
Richards,  Theodore  William,  S19 
Richter,  Hieronymus  Theodor,  254,  641, 

644-646 

Ridgeway,  William,  566 
Rinman,  Sven,  150,  159 
Ritthausen,  H.,  490 
Robinson,  W.  O.,  490 
Robottom,    Arthur,    his    explorations    of 

borax  in  Nevada  and  California,  583, 

584 

Roebuck,  Dr.  John,  186 
Roloff,  J.  C.  H.,  532 


908 


DISCOVERY  OF  THE  ELEMENTS 


Roscoe,  Sir  Henry  Enfield,  360-363,  619, 

626,  629,  684 

Rose,  Heinrich,  316,  341,  347,  348 
Rose,  Valentin  the  Younger,  265 
Rouelle,    Guillaume-Frangois,    115,    456, 

467 

Rouelle,  Hilaire-Marin,  467 
Rubidium,  631-634 
Ruby,  chromium  in  the,  278 
Riickert,  G.  C.  A.,  528 
Rumford  (see  Thompson,  Benjamin) 
Rupprecht,  Anton  von,  324,  526 
Russell,  Alexander  Smith,  824,  828 
Ruthenium,  440-447 
Rutherford,  Daniel,  205,  206,  208,  234- 

249 

Rutherford,  John,  235,  236 
Rutherford,  Sir  Ernest,  815,  816,  818 
Ryden,  Stig,  290,  299 

Sage,  Balthasar-Georges,  164 

Sainte-Claire  Deville,  Charles,  602 

Sainte-^Claire  Deville,  Henri,  550,  587, 
588,  602-606 

Sal  ammoniac,  188-190 

Salt,  461-464;  Glauber's,  466 

Saltpeter,  190^193,  211,  212;  as  distin- 
guished from  sodium  carbonate,  192 

Samaria,  712,  713,  717-720 

Sassolite  (see  Boric  acid,  natural) 

Sayre,  L.  E.,  517 

Scaliger,  Julius  Caesar,  408,  409 

Scandia,  708,  709 

Scandium,  677-683 

Scheele,  Carl  Wilhelm,  133,  170,  173, 
208,  213,  221,  222-225,  243,  252,  254- 
256,  260-262,  264,  456,  458,  514-517, 
551,  552,  729,  756,  758 

ScheeHte,  254-258 

Scheerer,  C.  J.  A.  Theodor,  678 

Scheffer,  Henric  Theophil,  416,  417 

Schiapparelli,  C.,  490 

Schmidt,  G.  C.,  560 

Schoolcraft,  Henry  R.,  151 

Schroeder,  Johann,  94 

Schrotter,  Anton  von,  135,  136 

Sdhiirer,  Christoph,  158 

Schultze,  M.  O.,  161 

Schwanhard,  Heinrich,  756 

Schweigger,  J.  S.  C.,  530,  531 

Scott,  Sir  Walter,  235,  236,  239,  247-249 

Seaborg,  Glenn  Theodore,  558,  869-871, 
875-879 

Searle,  Dennis,  co-discoverer  of  borax  in 
California,  583 

Sea  water,  boric  acid  in,  584,  585;  bro- 
mine from,  754;  magnesium  from,  528 


Sedative  salt,  574,  575 

Sefstrom,   Nils   Gabriel,   353,   354,   355, 
357-359,  684 

Segre,  Emilio  Gino,  862,  865 

Selenium,  306-318;  in  Chile,  315;  other 
sources  of,  316,  317;  uses  of,  317,  318 

Selenium  poisoning,  317 

Sempere  y  Guarinos,  J.,  412 

Serpentine,  523,  524 

Shepard,  Charles  Upham,  377 

Shu-Sha,  461 

Sicard,  Father,  188 

Sickingen,  Baron  Carl  von,  417 

Silica,  in  plants  and  animals,  588 

Silicon,  586-588;  preparation  of  first  crys- 
talline, 587 

Silliman,  Benjamin,  78,  376,  519 

Silliman,  Benjamin,  Jr.,  376 

Silver,    14;   mines,   16;   symbol,    15,   16; 
trees,  18 

Skillings,  E.  M.,  co-discoverer  of  borax 
in  California,  583 

Slevogt,  Johann  Adrian,  522 

Sloane,  Sir  Hans,  342,  372,  373,  377 

Smalt,  158,  159 

Smelters,  nickel,  166 

Smith,  Edgar  Fahs,  377;  his  picture  of 
Wohler,  600 

Smith,  J.  Lawrence,  387,  459,  706 

Smith,  Thomas  P.,  375 

Smithson,  James,  382 

Sobolevskii,  P.  G.,  428 
Soddy,  Frederick,  812,  820,  825-827,  828 
Sodium,  473-484;  in  basalt  and  lava,  466, 
467;  in  plants  and  animals,  467,  468; 
some  compounds,  460-468 
Sodium  carbonate,  as  distinguished  from 

saltpeter,  192 
Soderbaum,  H.  G.,  497 
Soret,  Louis,  711 
Southey,  Robert,  478 
Sowerby,  James,  166 
Spallanzani,  Abb6  Lazaro,  590 
Spectroscope,  Kirchhoff-Bunsen,  626 
Spectroscopic  analysis,  624 
Speter,  Max,  129,  137,  336,  717 
Sphalerite,  151 
Spodumene,  485,  489 
Stahl,  Georg  Ernst,  197,  198,  474,  507, 

590 

Steinkoenig,  L.  A.,  490 
Stibick-stone,  96 
Stock,  Alfred  E.,  768 
Stomach,  free  hydrochloric  acid  in  the, 

187 

Strabo  of  Amasia,  141 
Strassmann,  F.,  868 


INDEX 


909 


Straub,  Johann  Castor,  743 

Street,  K.,  Jr.,  876 

Stromeyer,  Friedrich  160,  161,  529-534, 
744 

Strontium,  517-521;  in  plants  and  ani- 
mals, 521 

Stratt,  John  William,  750,  781,  784,  785 

Suckow,  Georg  Adolph,  465 

Sulfur,  52;  as  an  element,  55;  in  animals, 
57;  in  Louisiana  and  Texas,  56;  in 
plants,  57 

Sulfuric  acid,  185,  186 

Sundstrb'm,  Anna,  Berzelius*  housekeeper, 
734 

Svab,  Anton  von,  150,  159 

Svedenstjerna,  E.  T.,  485 

Swedish  metals,  152-174 

Sweet,  Jessie  M.,  377,  378 

Sympathetic  ink,  160 

Szathmary,  Ladislaus  von,  324,  336 

Szilard,  L.?  860 

Tacitus,  Cornelius,  466 

Tacke,  Ida,  851-853 

Talbot,  William  Henry  Fox,  621,  622,  623 

Tannin,  383 

Tanning  agents,  382 

Tantalum,  345-352;  uses  of,  351 

Tassaert,  Citizen,  278,  279 

Technetium,  862,  863 

Telluric  screw,  654-656 

Tellurides,  natural,  in  the  United  States, 

305 
Tellurium,     303-305;     Klaproth-Kitaibel 

letters  on,  321-337 
Tennant,    Charles,    his    solid    bleaching 

powder,  735 

Tennant,  Smithson,  436-440 
Terbia,  705-707 
Texas,  sulfur  in,  56 
Thalen,  Tobias  Robert,  680,  681 
Thallium,  635-641;  effect  on  plants  and 

animals,  641;  in  pyrite,  641;  isolation 

of,  638 
Thenard,    Louis-Jacques,    482,    574-580, 

730,  732 

Thermometer,  description  of  by  Ruther- 
ford, 246 

Thompson,  Benjamin,  478 
Thompson,  S.  G.,  876,  879 
Thomson,  Thomas,  342,  348-350,  356, 

376,  384-386,  432,  488,  554,  696 
Tholde,  Johann,  190 
Thorium,  558-560 
Thorium  series,  824-831 
Thornton,  W.  M.,  Jr.,  550 


Thorpe,  Sir  Edward  (T.  E.),  358,  361- 

363,  434 
Thulia,  709-712 
Thurneysser,  Leonhard,  619 
Tin,  43;  dishes,  46;  plating,  46 
Tincal  (see  Borax) 
Titanium,  545-551;  in  plants  and  animals, 

549-551;  other  sources  of,  549 
Toland,  John,  521 
Townsend,  Joseph,  412 
Transuranium  elements,  867-876 
Travers,  Morris  William,  792-794-796 
Triads,  653 
Tritium,  205 

TroUe-Wachtmeister,  H.  G.,  495 
Troost,  Gerard,  488 
Tschirnhaus,  Count  Ehrenfried  von,  124, 

125 

Tungsten,  253-258 
Tungstic  acid,  255 
Tut-ankh-Amen,  506 

United  States,  natural  tellurides  in  the, 

305 
Uranium,    264-270;    Arfwedson's    paper 

on,  500,  501;  in  mineral  waters,  270 
Uranium  fission,  discovery  of,  860 
Uranium  series,  811,  812 
Urbain,    Georges,    720,    721,    846,    848; 

remarks  on  the  Curies,  810,  811 
Urdang,  Professor  George,  224 
Urey,  Harold  Clayton,  204,  205 
Urine,  experiments  on,  110,  111 

Valentini,  Michael  Bernhard,  522 
Valentinus,  Basilius,  98,  184-186,  190 
Vanadinite,  360 
Vanadium,  352-364,  392;  in  plants  and 

animals,  364;  isolation  of  metallic,  363 
Vanadyl  chloride,  362 
Vapor  calorimeter,  invention  of,  634 
Varvinskii,  I.  L,  428 
Vauquelin,  Nicolas-Louis,  270,  271-279, 

430,  437,  485,  544,  556,  566-568,  745, 

746 
Vegetable  ash,  iron  in,  36;  potash  from, 

455 

Vegetation,  83 
Verdigris,  23 

Vinegar,  183,  184;  manufacture  of,  184 
Vitruvius,  Marcus,  8,  42 

Wastfelt,  Amy,  502 

Wait,  C.  E.,  549 

Waitz,  Jacob,  160 

Wall,  M.,  457 

Wallerius,  Johan  Gottschalk,  135,  514,  528 


910 


DISCOVERY  OF  THE  ELEMENTS 


Washburn,  Edward  W.,  205 

Washington,  George,  experiments  of,  79 

Watson,  Richard,  147,  149 

Watson,  Sir  William,  411,  412,  414,  415 

Watt,  James,  516 

Webb,  D.  A.,  364 

Weintraub,  E.,  580 

Weisbach,  Albin,  686,  687,  689 

Weiss,  Colonel  Jacob,  75 

Weisbach,  von  (see  Auer,  Carl) 

Wenzel,  Carl  Friedrich,  759 

Werner,  Abraham  Gottlob,  286,  287 

Werner,  L.  B.,  872,  875 

Wharton,  Joseph,  167 

Whitaker,  Arthur  P.,  290 

White  lead,  42 

Wicker,  Henry,  521 

Wiegleb,  Johann  Christian,  543,  758 

Willemite,  151 

Willis,  L.  G.,  549,  586 

Willstatter,  Richard,  528 

Winderlich,  Rudolf,  94 

Winkler,  Clemens  Alexander,  254,  645- 

647,  683-689 

Winthrop,  Francis  B.,  378,  379 
Winthrop,  Governor  John,  the  Younger, 

339,  340,  376 
Winthrop,  John  (Grandson  of  Gov.  John 

Winthrop),  376-378-380 
Wiseman,  Benjamin,  370 
Withering,  William,  515,  516 
Witherite,  515,  516 
Wittich,  Ernst,  394 


Wohler,  Friedrich,  315,  316,  353-355, 
357,  360,  425,  444,  447,  487,  549,  550, 
557,  569,  595-598,  600,  601,  602,  700, 
701,  703;  his  picture  of  Hisinger's 
home,  553,  554 

Wolframite,  256,  257,  288 

Wollaston,  William  Hyde,  171,  340,  347, 
383,  423-426,  429-433,  434,  436,  437, 
439,  440,  534,  549 

Wood,  Charles,  409,  414 

Woulfe,  Peter,  254 

Wu,  C.  S.,  862 

Wulfen,  Abbe  F.  X.,  264 

Wulfenite,  264 

Wurtz,  Adolph,  673 

Xenon,  795-797 

Ytterbia,  708,  709,  720-724 
Yttria,  699,  705-707 

Zaffer,  153,  154;  as  described  by  Pomet, 
155,  156 

Zinc,  141-152;  as  a  by-product,  145;  as 
described  by  Geoffrey  the  Elder,  144, 
145;  description  of  Goslar  works,  145, 
146;  famous  American  mines,  150,  151; 
improvement  of  metallurgical  process 
of,  150;  in  plant  and  animal  nutrition, 
151,  152;  metallic,  142;  prepared  from 
blende,  149 

Zinc  ores,  cadmium  from,  534 

Zincite,  150 

Zincken,  Johann  Karl  Ludwig,  316 

Zinin,  Nikolai  Nikolaevich,  446 

Zirconium,  543-545;  uses  of,  545 


112  109 


CD 

3